US2179234A - Manufacture of multicolor photographs - Google Patents

Description

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Patented Nov. 7-, 1939 PATENT 0F 2,179,234 Fl CE MANUFACTURE OF MULTICOLOR PHOTOGRAPHS Wilhelm Schneider, Dessau, Germany, assignor, by mesne assignments, to Agfa Ansco 001130! ration, Binghamton, N.

Delaware Y., a corporation of No Drawing. Application September 11, 1936,

Serial No., 100,319. 1935 In Germany October 3,

r 4 Claims. .(01. 95-2) My present invention relates to the manufacture of multicolor photographs.

One of its objects is an improved process of producing multicolor photographs. Another object is a process of producing a multicolor photograph by a single development in color. Another object is a process of producing a multicolor photograph by a single exposure and a single development in color. Further objects will be seen 7 from the detailed specification following hereafter.

It has long been known that one can develop exposed photographic silver halide emulsions to a color-picture instead of the usual black silverpicture by using either certain developers (pyrogallol, indoxyl, thioindoxyl or thelike) which are oxidized to sparingly soluble colored bodies by exposed silver halide, or by adding to certain developers, for example para-dimethyl-aminoaniline, substances which couple to form sparingly soluble colored bodies with the oxidation products of the developer produced during'the development. In the latter case it has been proposed to incorporate the coupling components in the sensitive layer itself. these processes have been conceived particularly for the purpose of multicolor photography, they have not passed into practice because they are much too detailed. For this reason, lately a variantof the second process referred to above has been proposed, which requires a large number of successive treatments with liquid of a three-layer film. I

The present invention relates to the treatment of a photographic layer in a simple manner to produce two-color or multicolor pictures without any developing operation in excess'of that for normal black-a'nd-white development.

Layers suitable for the invention are of the kind which have been described in the co-pending application Ser. No. 90,726 filed July 15, 1936. They are silver halide emulsions, to which has been added, for example, a substance obtainable by the reaction of a compound which by known reactions is capable of forming dyestuffs, for example an amine, a phenol, an aminophenol, a naphthol or an amino-n'aphthol, or a compound having a reactive methylene-group, with a highly polymeric carboxylic acid or a derivative thereof, for instance, the condensation product from U polyvlnyl-maleic-acid-anhydride and p-amino- .phenyl-3-methylpyrazolon having probably the formula:

(on on-on-on), coon com;

and the condensation product from polyvinyl- Although, obviously,

maleic-acid-anhydride and m-arninophenol having probably the formula (on-oH-on-on coon ,OONH- So also the silver halide emulsion layers described in the copending application Ser. No. 72,718 filed April 11, 1936, may be used. These contain as coupling components for the color development such compounds as are fast to diiiusion in the binding agent used, for instance the gelatin or the like. Suitable groups which determine such fastness to diffusion are, for instance, diphenyl, stilbene, azoxy-benzene, hydroxynaphthoic acid amide, diaryl-urea, benzthiazole and certain phenols, aminophenols containing substituents in the 3:5-position and the like. Color-forming components in which these groups are introduced are, for example, phenols, anilines, naphthols,

naphthylamines, amino-naphthols; also all substances which have a reactive methylene-group, for example an acetoacetic ester, a cyanoacetic ester, a benzoyl-acetic ester, hydrindene, pyrazolone, cumaranone. Further suitable components are for instance a-hydroxynaphthoic-acid-benzi- [m hydroxyphenylaminocarboyll diphenyl or the like.

Finally, there are applicable according to the invention emulsion layers in which there are incorporated color-formers containing an aliphatic hydrocarbon chain of more than 5 carbon atoms. Such layers are described in the co-pending application Ser. No. 94,340 filed August 5, 1936. All

these layers have the property that the incorporated color-former is converted into dyestuff by 'a secondary process during the color develop ment and is more strongly held in the light-sensitive layer, which generally comprises gelatin, than has been the case with the bodies hitherto proposed for the purpose; thus they withstand the usual photographic baths. treatment nor inthe subsequent washing with water are they dissolved or washed off. Only under these conditions is it possible to conduct in a single operation a development of all the contributory colors in three superimposed layers.

In the process there is provided a multilayer Neither in this film consisting, for instance of two or three lightsensitive layers arranged on oneor both faces of a' single support and selectively color-sensitized,

and capable of being developed to a color corresponding with its range of color sensitivity; this film is exposed in a photographic or cinematographic camera and then developed with 2. normal black and white developer to produce a nega tive. For this development there must only be used a developer which does not react with the coupling components incorporated in the layers, for instance, ,amidol, para-methylaminophenol, or hydroquinone. After the development of the black and white negative the film, without being fixed, .is exposed to the general illumination, whereupon the residual silver halide is developed with a color-forming developer, ,for instance para-dimethylamino-aniline. The general illumination and color development following the first black-and-white development may advantageously be combined by merely conducting the color development in bright light.

In the second developing operation there is produced in each layer of the multicolor film a picture in the component color allotted to this layer; for example, in a 3-layer film there are obtained at once 3 component pictures of correct color and superimposed. After the second development the silver present in the layers may be removed by any of the usual solvents for silver. It is also possible to remove already the silver formed in the first developing operation by means of the known silver dissolving agents.

.The process may similarly be conducted for producing copies by copying, optically or in contact, an exposed film made by the process above described, enlargement or diminuation being used if desired, on such a material and developing to a colored positive picture in the manner described.

As a specific example, a support, for instance a Celluloid film, carries on its front face an orthochromatically color-sensitized layer in which incorporated diphenylcarboyl-4.4'-di-(paraamino-1-phenyl-3-methyl-5-pyrazolone) as a red developing component. Over this layer is a not specially sensitized layer which contains as the yellow developing component dibenzoylaceticbenzidide-3.3-dicarboxylic acid and at the same time a yellow filter color, for example tartrazine. On the back of the film is a layer of emulsion which is sensitive to red light and contains as the blue developing component 4.4"-di-1-hydroxy-2- naphthoylamino) -diphenyl. Then this film is exposed and first developed for 10 minutes in an amidol developer (200 cc. of water, 1 gram of amidol, 10 grams of sodium sulfite crystals, 0.2

gram of potassium bromide) and then washed for 5 minutes and further developed for 10 minutes in daylight with dimethylaminoaniline (200 cc. of water, Zgrams dimethylaminoaniline, 6 grams calcined sodium carbonate); after washing for 15 minutes and then removing silver by means of Farmer's reducer, for example 200 cc. of water, 20 grams of sodium thiosulfate and 2 grams of potassium ferri-cyanide, a colored positive is obtained.

What I claim is:

1. A process of producing multicolor photographs which comprises producing a multilayer film having incorporated in the several gelatine silver halide emulsion layers a dye component capable of forming a dye with a developer adapt- -solved form of diffusing components and removing the developed silver from said film.

2. A process of producing multicolor photographs which comprises producing a multilayer film having the emulsion layers arranged in superposition 0n the same side of the support and having incorporated in the several gelatine silver halide emulsion layers a dye component capable of forming a dye with a developer adapted for color development said dye components although soluble in aqueous photographic developing solutions being of such molecular constitution that they are incapable in such dissolved form of diffusing in gelatine in any photographic treating bath, exposing said multilayer film to a colored object,-developing the exposed film in a developer not capable of forming a color with said dye components, exposing said multilayer film a second time simultaneously developing all the layers of the exposed film in a developer capable of forming dyes with said dye components and removing the developed silver from said film.

3. A process of producing multicolor photographs which comprises producing a multilayer film having incorporated in the several gelatine silver halide emulsion layers a dye component capable of forming a dye with a developer adapted for color development, said dye components although soluble in aqueous photographic developing solutions being of such molecular con-.

stitution that they are incapable in such disin gelatine in any photographic treating bath, exposing said multilayer film to a colored object, developing the exposed film in a developer not capable of forming a color with said dye components, and then simultaneously developing all the layers of said film in bright light in a developer capable of forming a dye with said dye components and removing the developed silver from said film.

4. A process of producing multicolor photographs which comprises producing a film having one side coated with an orthochromatically sensitized silver halide emulsion layer containing diphenyl 4.4" (para amino 1 phenyl 3 methyl-5-pyrazolone) and this emulsion layer with a silver halide emulsion layer which has not been specially sensitized and containing dibenzoylacetic-benzidide-3.3-dicarboxylic acid and a.

yellow filter dye, and the other side with a silver halide emulsion layer sensitized to red and con taining 4.4-di-(1 hydroxy-2-naphthoylamino)- diphenyl, exposing this film to a colored object,

simultaneously developing all the layers of the