US2376822A - Production of color photographic images - Google Patents

Production of color photographic images Download PDF

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Publication number
US2376822A
US2376822A US438566A US43856642A US2376822A US 2376822 A US2376822 A US 2376822A US 438566 A US438566 A US 438566A US 43856642 A US43856642 A US 43856642A US 2376822 A US2376822 A US 2376822A
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azo
image
acid
silver
solution
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US438566A
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Schneider Wilhelm
Frohlich Alfred
Neugebauer Gustav
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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
    • G03C7/46—Subtractive processes not covered by the group G03C7/26; Materials therefor; Preparing or processing such materials

Definitions

  • the methods hitherto known can be avoided in the photographic production of azo dyestufl images by producing an azo dyestuii insilver halide emulsions by azo dyestufi coupling from a'diazotizable amine and a compound capable of azo coupling, at least one of these reactants already being in a non-diffusing form in the layer, at the places free from silver after development of the silver image and, if necessary, after fixing and then removing the image silver and, if necessary, the residual silver salts in a manner known per se.
  • an azo dyestufl is formed at the points free from silver in a photographic layer,-which contains an amine capable of being diazotized besides a silver image, after the treatmerit of the layer with a hydrochloric acid-nitrite solution and the solution of an azo coupling component not containing a salt of a heavy metal or any other additional compound.
  • the course of this reaction is also complete when the photographic layers already contain an azo coupler in a condition fast to diffusion, for instance, a derivative of naphthol or of pyrazolone in which case it is immaterial whether or not the nitrite solution contains a salt of a heavy metal.
  • a silver halide emulsion layer containing a-hydroxy-p-naphthoyl-2-amino-3-palmityl amino toluidine-5-sulfonic acid as the azo coupler is exposed by means of a gray wedge.
  • the layer is bathed in a 1% solution of dehydrothiotoluidine-4-sulfonic acid for 20 minutes, washed, then treated with a solution consisting of 8 cc. of 1/1 normal sodium 'nitrite solution and 1000 cc. of 1/25 normal hydrochloric acid, subsequently washed again for a short time, and finally treated in a l 1 normal sodium acetate solution.
  • a red dyestuff is produced thereby in the layer at the places free from silver and a reverse dyestufi image of the original silver image is obtained after the removal 0! the silver either with a solu- 55 tion of potassium cyanide or with Farmer's reboth sides of the support.
  • the ,diazotizing solution does not notably influence the non-diffusing azo coupling components being in the layer, for instance, naph thols or compounds having reactive methylene group such as pyrazolones
  • Such material is suited to the exposure as well as the reproduction of multi-color images.
  • the mixture is cooled to 15 C., filtered and added to 300 cc. of a silver halide emulsion.
  • the layer cast therefrom is exposed, developed, and fixed whereupon it is treated in a nitrite solution having the composition described in the above-mentioned example. After a short washing the layer is brought into a 1/1 normal sodium acetate solution whereby the dyestufl coupling is effected. After the removal of the silver with a usual bleaching bath or a potassium cyanide solution one obtains a red dyestuil image which represents a reverse image of the silver image as first formed. If an acetic acid solution is used for the diazotization instead of the hydrochloric acid solution, the dyestuff coupling is already effected in the diazotizing bath.
  • pling bath may be omitted if acetic acid is sub- 1 stituted for the hydrochloric acid in the diazotizing bath since in this case the coupling is al- After exposure, development After the removal of the silver The acetate bath as the couready effected in the diazotizing bath.
  • 5 gradation of the dyestuif image may essentially be influenced by varying the concentration of the salt of the heavy metal in the diazotizing solution.
  • the process of the present invention substanstart be incorporated in the layers.
  • both dyestufi formers can be added to the silver halide emulsion layers in the present process, 1. e., the azo component as well as the diazo component, the latter in the form of an amine capable of undergoing the diazo reaction.
  • the desired dyestuif in each layer of the multi-layer material from components which yield not only the desired color but the most favorable tint.
  • each dyestuff is formed in the single layers from different azo components and different diazo components as, for instance, the yellow dyestuff from 1-phenyl-3-heptadecyl-5-pyrazolone- 3-sulfonic acid and the tetrazotized urea obtained with two mols of sodium p-aminobenzoyl-p-phenylene-diamine-sulfonate, the purple dyestuff' from di-(2.3-hydroxynaphthoyl) -benzidine and the tetrazotized urea obtained with two mols of sodium p-aminobenzoyl-p-phenylenedia mine sulfonate and the blue-green dyestuif from the tetrazotized octylether of dihydroxybenzidine and 8 stearyl amino-naphthol -2.4 -disulfonic acid.
  • the silver halide emulsion layers containing the amines capable of being diazotized and the azo coupling compounds are sensitized to different spectral ranges. If desired, the layers are combined with filter layers and anti-halation layers and arranged on one or both sides of a support.
  • the red and yellow images may be'produced in two layers which are on one side of the support whereas a Prussian blue image may be obtained in a third layer on the other side of the support by the toning process, this third layer advantageously serving for recording a sound track.
  • the red and yellow images may be'produced in two layers which are on one side of the support whereas a Prussian blue image may be obtained in a third layer on the other side of the support by the toning process, this third layer advantageously serving for recording a sound track.
  • present process is especially suitable for the simultaneous production of sound track and image record when such azo dyestuffs are produced as are capable of being after-treated with a salt of a heavy metal as, for instance, derivatives of salicylic acid suitable for after-chroming.
  • a salt of a heavy metal as, for instance, derivatives of salicylic acid suitable for after-chroming.
  • dyestuffs which contain salts of a heavy metal and show anespecially favorable capability of absorbing the light rays affecting the photo-cells.
  • each of the three layers contains both azo dyestuff components already before exposure.
  • the third layer contains only one azo coupling component.
  • This process is so carried out that the two azo dyestuff images are first produced in the two layers which contain both coupling components whereupon the third layer is bathed in the solution of a diazotizable amine as, for instance, dehydrothiotoluidine-sulfonic acid and after washing ispresent invention.
  • a diazotizable amine as, for instance, dehydrothiotoluidine-sulfonic acid and after washing ispresent invention.
  • combinations of dif-' ferent modifications of the present process as well as for other processes are possible whereby numerous ways for reaching the desired color tones are given.
  • diazo components all monovalent and bivalent diazotizable amines as, for instance, dehydrothiotoluidine, nitroaniline, benzidine and methyloctadecylstearylanilinesulfonic acid are suitable for the process of the present invention.
  • azo components all compounds capable of coupling such as phenols and amines are to be mentioned. These compounds may carry radicals effecting fastness to diffusion and watersolubilizing groups.
  • monoor polyazo dyestuffs can be formed.
  • the dyestuff formers may be rendered fast to diffusion with respect to gelatin in different ways.
  • molecular groups are disclosed,in Patent 2,179,238, dated November 7, 1939, and which impart to the dyestuif substantive properties with respect to cotton as, for instance, one or several diphenyl radicals, hetero- Ill cylic radicals or stilbene radicals may be introduced into the molecule of the dyestuff former.
  • the radicals effecting fastness to diffusion include, for instance, long straight carbon chains, high molecular weight fatty derivatives or long-chain polymers as, for instance, polyethyleneimine. and many polymerizates and mixed polymerizat'es of vinyl derivatives falso together with unsaturated, acids such as maleic acid and crotonic acid).
  • the dyestufi formers made non-diffusing in this way sometimes show the property of producing no real but only colloidal solutions. Also a certain diilicult solubility in aqueous media can prevent the difl'usionfrom the layers. Further diffusionpreventing means are the known precipitating salts.
  • non-diffusing dyestuif formers may be incorporatedinto the silver halide emulsions in the presence of wetting or dispersing agents as described in U. 9. Pat. 2,186,717 or in the presence of bile acids or salts thereof as described in U. 8.. Patent 2,324,831.
  • diazo compounds may also be used in the present process which step leads to a further simplification and. possibility of variation.
  • the photo-- graphic layers whichcontain an azo component capable of coupling and conveniently in a dimcultly diffusing condition are treated in the solution of a diazo compound, if necessary, in the presence of a salt of a heavy metal as, for instance, potassium ferricyanide, copper sulfate and sodium chloride or copper chloride.
  • a salt of a heavy metal as, for instance, potassium ferricyanide, copper sulfate and sodium chloride or copper chloride.
  • diazo solutions there are suitable all solutions of diazotized amines which may contain a stabilizer for increasing the stability thereof. It is, however. also possible to incorporate these diazo compounds into the layers, the only slowly coupling stabilized forms of the diazonium compound and the diazotates being especially suitable. In this case the coupling is accomplished in.
  • a silver halide emulsion layer which contains 1-phenyl-3-heptadecyl-5 pyrazolone-3' sulfonic acid as a coupling component is exposed, developed. fixed and then treated in cc. of a 1% solution which contains 1 cc. of a 10% copperchloride solution.
  • a yellow dyestuff image is formed at the places free from silver in a short time.
  • As to-the multi-color image a.
  • multi-layer material containing different dyestuff formers in the single layers for instance, 1-phenyl-3-hepadecyl 5 pyrazolone-3'-sulfonic acid for the yellow image, 2.3-hydroxynaphthoylbenzidide for the purple image and 8-stearyl-aminonaphthol-2.4-disulfonic acid for the blue image is treated after exposure and development of the partial silver images with a suitable diazo solution, for instance, with tetrazoof p nitrobenzene diazoniumchloride tized benzidine or dianisidine whereby the reversed dyestuil images of the original partial silver images are produced.
  • a suitable diazo solution for instance, with tetrazoof p nitrobenzene diazoniumchloride tized benzidine or dianisidine whereby the reversed dyestuil images of the original partial silver images are produced.
  • This modification may also be combined with those already mentioned above in any way in whichcase it is also possible to produce some partial color images by means of a dlazotizing I multi-color negatives or partial sensations and it 1 is possible to work up the photographic material for exposure as well as copying according to the present process.
  • the silver images at first produced may be obtained by simple or reverse development.
  • Dyestufi formers especially suitable for the process of the invention further include the folj lowing compounds: diaminobenzoyl compounds of the aminonaphthol-sulfonic acids and -carboxylic acids, naphthylaminosulionic acids and -carboxylic acids, cresotic acids, diaminocarbazoledisulfonic acids, pyrazolones and the ureas of 1 the aminobenzoyl compounds of the mentioned coupling components.
  • diaminostilbenes, benzidines and similar compounds which may be substituted at any positions 1 by any radicals capable of .diazotizing or couling, if desired, are of especial importance.
  • Such 1 compounds are, for instance, the urea from p-ami- 1 nobenzoyl-p-aminobenzoyl-I-acid and the urea from p-aminiobenzoyl-p-phenylenediamine sulfonicacid.
  • the following compounds are suited: aromatic hydroxycarboxylic acidamides as, for instance, hydroxynaphthoic acidarylide, hydroxyanthracenecarboxylic acidarylide, hydroxycarbazolecarboxi ylic acidarylide, hydroxynaphthocarbazolecarbox- 1 ylic acidarylide, amides of the ketocarboxylic acids as, for instance, terephthaloyl-acetic acidanilide,
  • couplers heterocyclically substituted l come into question for the present invention such pler containing an acid group and a diilusionpreventing amino group such as a-hydroxynaphthoyldodecylamine-4-sulfonic acid, 2.3-hydroxynaphthoic acldabietinylamide, 2.3-hydroxyanthracenecarboxylic acidoleylamide-w-sulfonic acid e or the esters or amides of color couplers containing hydroxyor amino groups and diffusion-preventing substituents containing at least one acid group as, for instance, 1-stearylamino-8-naphthol-ZA-disulfonic acid, palmi'tylaminophenylmethylpyrazolonesulfonic acid, undecanoylaminobenioylacetylanthranilic acid, 2-laurylamino-8- naphthol-fi-sulfonic acid, moreover compounds as, for instance,
  • Such compounds are, for instance, a colorcousaid diazotizable amine and effecting coupling of the diazotized amine and said other component in a coupling bath consisting of an aqueous solution of a water-soluble salt of an alkali and an organic acid.
  • an acidified aqueous nitrite solution to convert the amine into a diazonium compound, and coupling said compound with'said azo coupling component by means of a bath consisting ofan aqueous solution of a water-soluble salt of an alkali and an organic acid to form image only.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US438566A 1940-10-22 1942-04-11 Production of color photographic images Expired - Lifetime US2376822A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2514234A (en) * 1939-08-09 1950-07-04 Chromogen Inc Process for the manufacture of color photographic images
US2616806A (en) * 1949-03-04 1952-11-04 Gaspar Process for the manufacture of colored photographic images
US2629658A (en) * 1948-08-11 1953-02-24 Gen Aniline & Film Corp Silver halide emulsions containing nondiffusing azo dyes
US2644753A (en) * 1948-11-05 1953-07-07 Azo dyes and their use in color
US2653874A (en) * 1949-04-15 1953-09-29 Bela Gaspar Process for the production of color photographic images
US2671023A (en) * 1949-12-16 1954-03-02 Gen Aniline & Film Corp Preparation of azo dye images in photographic materials
US3338711A (en) * 1962-11-15 1967-08-29 Du Pont Process for forming azo dye photographic images

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2514234A (en) * 1939-08-09 1950-07-04 Chromogen Inc Process for the manufacture of color photographic images
US2629658A (en) * 1948-08-11 1953-02-24 Gen Aniline & Film Corp Silver halide emulsions containing nondiffusing azo dyes
US2644753A (en) * 1948-11-05 1953-07-07 Azo dyes and their use in color
US2616806A (en) * 1949-03-04 1952-11-04 Gaspar Process for the manufacture of colored photographic images
US2653874A (en) * 1949-04-15 1953-09-29 Bela Gaspar Process for the production of color photographic images
US2671023A (en) * 1949-12-16 1954-03-02 Gen Aniline & Film Corp Preparation of azo dye images in photographic materials
US3338711A (en) * 1962-11-15 1967-08-29 Du Pont Process for forming azo dye photographic images

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FR884372A (fr) 1943-08-11
CH231269A (de) 1944-03-15

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