US2179228A - Process of color photography and material therefor - Google Patents

Description

Nov. 7, 1939. J. EGGERT ET AL i 2,179,228

PROCESS OF COLOR PHOTOGRAPHY AND MATERIAL THEREFOR Original Filed March 12, 1935 In vemors t By Aorneys a what' T Patented Nov. 7, '1939` UNITED STATES PROCESS OF COLOR.'` PHOTOGRAPHY 4 MATERIAL THEREFOR vaNn John Eggert, Leipzig-Gomis, and Alfred Froehlichk and Bruno Wendt, Dessau, Germany, assignors, l by mesne assignments, to Agfa Ansco Corpora.

tion, Binghamton, N. Y., a corlmration` of Dela- Application March 12, 1935, 'serial No. 10,704. Renewed April 11, 1939. In Germany March 16, 1934 l5 Claims.

Our present invention relates to color photography.

Une of its objects is to provide an improved process of color photography. `Another object is a material for this improved process. Further objects will be seen from the detailed specication following hereafter.

For the production of colored photographic pictures by color synthesis `by means of azo-dyestuffs there have hitherto been available. two principal procedures. One procedure depends on the use of a diam-component which is not stable towardsr light (diazotype process), whilst in the other use is made of the silverimage in order to produce a colored image by way of a reactive silver compound. Particularly in the latter case it is endeavoured to incorporate one or both of the dyestui components in the light-V sensitive layer as far as possible in a water insoluble, stable form resistant to the development and fixing baths, and in such a manner that the transparency, natural sensitivity and artificial sensitization of the layer are not diminished.v

It has'been proposed, for example, to add the dyestui components to the photographic layer in the form of compounds insoluble in water, `such as metal compounds, salts of organic acids'or, in

the case of acid components, in the `formof esters,

anilides or the like. These compounds are to be nely dispersed, forI example, by introducinginto the gelatin an alcoholic solution of the compound which is insoluble inwater, so that the' compound is precipitated in the photographic layer. In this manner it is possible to incorporate the compounds in the gelatin in such a fine state of distribution that notwithstanding the insolubility of the compound in water the gelatin dries to a, transparent layer. .Another procedure for adding dyestuff components to the gelatin in water insoluble form makes use of coupling components which can be fixed by mordanting. Such coupling components, for example, naphthol,

chromotropic acid or the like, can be xed on the gelatin with the aid of a metal oxide and provided that the component has a suitable constitution the gelatin will dry to a layer clear as glass.

The present invention is based on the dis covery that it is possible to incorporate in the photographic layer azocomponents from aqueous solutions in such a manner thatv they are resistant towards the usual photographic baths by choosing those azo-dyestuff components which have substantive properties with respect to the layer. The addition of these substantive comu pounds naturally does not in any way impair the served, since in contrast Vto other processes the compounds are not distributed heterogeneously inthe layer but are actually dissolved in the gelatin.

The' procedure for carrying out the invention may consist for example, in adding to a solution of gelatin or the like a solution of an azo-component or ,diazo-component which is substantive towards gelatin, whereuponthe gelatin is thoroughly washed with water and then worked up in the usualmanner. It is also possible totreat algelatin layer o1 a foil of gelatin with a solution of one ofthe aforesaid dyestui components. ln both cases the gelatin, in the language of the dyeing industry, is dyed by the dyestuff component even though in the case of a colorless component the layer does not acquire a color which can be perceived by the eye. Y

In order to produce a colored image .use may be made of any'of the known processes.

For instance gelatin which has been rtreated. with Vboth dyestui components may be worked up into a silver halide emulsion. .After exposure the silver image is bleached in a bleaching bath which at the same time tans and hardens the gelatin .atthe exposedparts of the layer. If now the layer is treated with an acidifled solution of sodium nitrite, Adiasotization and formation of a dyestuif occur at thoseparts of the picture area which are `not hardened and are therefore accessible to the action of the nitrite solution. ln this manner a red vpicture may be obtained by means of 2 S-hydroxynaphthoic-acid-a-naphthalide corresponding with the formula l -COf-NH and `u r e a-bis- (para-aminobenzoyl-para-phenylene-diamine-sulfonic acid corresponding with the formula Y In this method it is also possible to incorporate in the gelatin only the eze-component and to use instead of the nitrite solution a diam-solution. Thus by dyeing the gelatin with 2:3-hydroxyn naphthoic-acid-a-naphthalide and treating the layer with tetrazotized dianisioline there is obtained a blue picture. Another procedure may consist in dyeing the gelatin only with the azocomponent and then either converting the silver image into an anti-diazotate image (for vexample according to U. S. Patent No. 1,963,197) or caus- 5 ing the silver halide to adsorb a diazonium compound and after washing forming the dyestui in a coupling bath. For example, it the gelatin is dyed with di-ortho-sulfobenzylidene-4:4diami nodiphenylurea corresponding with the formula S 03H B 01H a yellow picture may be obtained by means o! the anti-diazotate of -naphthylamine. Furthermore, there can be used instead of the 2:3-hydroxynaphthoic acid arylides similarly constituted hydroxycarboxylic acid amides, for instance, arylides of 2:3-hydroxyanthracenic acid, arylides o of hydroxycarbazole carbonio acid, arylides of 0 hydroxynaphthocarbazole carboxylic acid (a. compound of this group corresponds with the formula C O--NH or arylides of terephthalacetic acid (a compound of this group corresponds with the formula arylides of the hydroxycarboxylic acid of diphenylene oxide and diphenylene sulfide (compounds of this group corresponds with the formulae on oom v (Jo-NH@ CEs' on ci s (Jo-NH@ furthermore the arylides of -naphthindole-2- 50 phenyl-7-hydroxycarboxylic acid (a compound of this group corresponds with the formula and as well as pyrazolones from Z-p-aminophenylthiazoles (a compound of this group corresponds with the formula NBC-CH:

CO- Ha) and 2-hydroxyuoren, -hydroxyanthracen, hy-l droxychrysene and others. A like picture is obtained ii the silver halide is caused to adsorb para-nitro-benzenediazoniumchloride and coupling is then brought about.

Yet a furth'er procedure in accordance with the invention consists in dyeing the gelatin with both dyestuff components and then converting the silver image into an insoluble nitrite compound.

. If now diazotization is brought about in any suit- 10 able manner the dyestufl is formed at the places in the layer corresponding with the image. In this manner a. red picture may be produced, for example, from the urea from para-dimethylaminobenzoyl-para-aminobenzoyl-2-amino--naph- 15 thol-'I-sulfonic acid corresponding with the formula Ho, NH-coONn-oo-Omcnm pounds of aminonaphthol sulfonic and carboxylic acids (a compound of this group corresponds with the formula -O-NH-oo-O-Nm) of naphthylamine sulfonlc and carboxylic acids (a compound of this group corresponds with the formula of cresotinic acid and of diaminocarbazole disul- 4 ionic acid (a. compound of this group corresponds with the formula HO: N 70 H Ganga as well as the ureas from the amnobenzoyl compounds o! the aforesaid coupling components (a 75 amazes compound of this `group corresponds with the H. Oi particular interest areturther4 the benzoyl, benzyland benzylidene-compounds of diaminodiphenyl ureas, of diaminodiphenyl-thioureas, of diaminostilbenes, of'benzidines and similar compounds (compounds of these groups with the formulae SOsH correspond SOaH so i

including compounds containing any substituents in any positions. J

The invention is of particular importance in its application to the production of photographs 35 in natural colors. If there are cast in superimposed relationship emulsions of which each vis sensitized for one of the primary colors and is dyed with appropriate dyestuff components, the

color synthesis can be conducted in the layers in ample, in the case of a three-color rllm two color images may be produced on one side of the support byI the process of the invention, whereas the remaining color image may be produced, for example, on the other side of the support by toning or on the same side by an imbib-ition process.

The invention comprises a photographic material consisting of a support coated on one or both sides with one or more layers of silver halide gelatin emulsion which is or are dyed with an azo-dyestuff component or components substantive with respect to the layer.

The following examples serve to illustrate the invention:

dll

Example 1 A nlm coated with a layer of gelatin is bathed in the following solution:

whereupon the material is Washed with Water for about 1/2 hour. Then the sheet is bathed in a solution of p-diphenylamindiazonium sulfate and is dried. After exposure under an original and treatment with an aqueous solution of ammonia or gazeous ammonia a blue picture is produced at the places which were not illuminated.

Example 2 l There is produced a solution of 10grams of p-dimethylamidobenzoyl-p-amidobenzoyl-(2-amino-5-naphthol-7-sulfonic acid) in 1000 cc. of water, with the addition of 10 cc. of a causticsoda solution of 20% strength.

In this solution a silver bromide emulsion layer is bathed for 10 minutes and washed with water for about 1 hour. An original is printed on this layer, and the layer developed, fixed and the silver image bleached by means of copper chloride. The bleached-out silver image is converted into naphthylamine-antidiazotate-si 1v e r 'by means ol an alkaline solution of -naphthylamine-antidiazotate-sodium and t h o r o u g h l y Washed.v When this picture is immersed into a solution of 1 gram of citric acid and 1 gram of potassium bromide, a red azo-dye picture is produced. The silver bromide is removed by fixing.

Y y Example 3 There is made a solution of 20 grams of 2.3hydroxynaphthoic-acid--naphthalide in 1000 cc. oi? Water and i l ce. o1 asolution of caustic soda of 20 strength.

The solution is filtered and mixed with a solution of grams of urea-bis-(p-amidobenzoyl-pphenylenediamine sulionic acid) in a quantity of Water as small as possible and a small amount oi caustic soda solution; a silver bromide emulsion layer is bathed therein for about 10 minutes,

washed with water for about 1 hour and dried.

When printing on this layer and converting the silver image in known manner into an insoluble nitrite compound, a red dye picture is produced by starting diazotization by bathing the layer in dilute acetic acid.

Example d l00 cc. of silver bromide emulsion are mixed with a solution of 0.5 gram of 2.3-hydroxynaphthoic-acid-a-naphthalide in l0 cc. of a caustic soda solution of 5% strength.

Furthermore there is addedl a solution of 0.3 gram of urea-bis-(p-amldobenaoyl-p h e n yl- The caustic soda is neutralized by means of acetic acid the emulsion solidified and washed with water. The emulsion is cast and the silver image produced in the emulsion layer by printing, developing and hiring is bleached with a bleaching bath having the property to tan the gelatin at the places of the picture. It the picture is treated with a solution of 5 grams of sodium nitrite in 200 cc. of acetic acid of 1% strength, a dye picture is produced from the two components at the non-hardened places.

Example 5 (a) l kilo of silver bromide emulsion is mixed with 5 grams of 2.3-hydroxynaphthoic-aci d-dianisidine dissolved in cc. of methanol 5 cc. of a caustic soda solution of 20% strength and neutralized with 15 cc. of acetic acid of 10% strength. This emulsion is sensitized for green.

(b) 1 kilo of silver bromide emulsionismixedwith 5 grams of urea from 1(3'amidophenyl)3 methyl-5-pyrazo1one by conversion with phosgene 25 cc. of methanol and 5 cc. of caustic soda solution of 20% strength are neutralized with 15 cc. of acetic acid.

lwhich is decolorized in the developer, and a panchromatic silver bromide emulsion is cast on the filter layer. Now a partial color picture is produced in each of' the layers, but after development and fixing only that side of the film is bleached to which the two emulsion layers (a) and (b) have been applied. The bleached-out silver .pictures are converted into -naphthylamineantidiazotate-silver pictures in the manner indicated in Example 1. If these pictures are treated with the solution of coupling component indicated in Example 1,.a yellow dye picture is produced in the layer (a) and a red dye picture is produced in the layer (b). The silver picture on the opposite side of the support is converted into a blue picture by dye-toning, for instance, an iron blue picture.

In the single iigure of the accompanying drawing there is shown a photographic material accompanying to this invention. The support a is provided with a photographic layer dyed with a compound having substantive properties with respect thereto.

What we claim is:

1. A process of producing color photographs, which comprises incorporating in a silver halide gelatin emuisiona coupling component of an azo dye, said coupling component having a chemical constitution which imparts to said component substantive properties towards the gelatin, forming a light-sensitive layer from said emulsion, exposing said layer to light controlled by an lobject tobe reproduced, developing the latent silver image, and causing said coupling component to react with a diazo compound, thereby producing an aZo-dyestuff picture in situ with the silver picture.

2. A'process of producing color photographs, which-comprises treating a silver halide emulsion layer with a solution of a coupling component of an azo dye, said coupling component having a constitution which imparts thereto substantive properties towards the gelatin, forming a light-A sensitive layer from said emulsion, exposing said layer to light controlled by an object to be reproduced, developing the latent silver image, and causing said coupling component to react with a diazo compound, thereby producing an azo-dyestuff picture in situ with the silver picture.

3. A process of producing color photographs, which comprises treating a gelatin solution containing silver halide with a solution of a coupling component having a chemical constitution which imparts thereto substantive properties with respect to the gelatin, forming a light-sensitive layer from said emulsion, exposing said layer to light controlled by an object to be reproduced, de-

veloping the latent silver image, and causing said coupling component to react with a diazo compound, thereby producing an azo-dyestui picture in situ with the silver picture.

. 4. A light-sensitive photographic element comprising a support and at least one silver halide emulsion layer capable of being converted into a colored picture by exposure to light, development and treatment with a diazo compound, said silver halide emulsion layer containing a coupling component of an azo dye; said coupling component having a chemical constitution which imparts thereto substantive properties with respect to the l which comprises incorporating in a silver halide gelatin emulsion a diazo compound and a coupling component of an azo dye, said diazo compound and said coupling component having a chemical constitution which imparts thereto substantive properties towards gelatin, forming a light-sensitive layer from said emulsion, exposing said layer to light controlled by an object to be reproduced, developing and fixing said layer, bleaching said layer in a bath which has at the same time a tanning and hardening action on the gelatin of the exposed parts of the layer, and treating said layer with an acidiiied solution of sodium nitrite.

6. A light sensitive material for color photography comprising a support and a silver halide gelatine emulsion thereon, containing an organic colorless dyestui component capable of reacting with a further component to produce a dyestui image, said first component having a chemical constitution which imparts thereto substantive properties with respect to the gelatine.

7. A light sensitive material for color photography comprising a support and a silver halide gelatine emulsion thereon, containing an organic colorless dyestuff component capable of reacting with a further component to produce a dyestui image, said first component containing an organic group which imparts to said component substantive character with respect to the gelatine.

8. A light sensitive element as defined in claim 6 wherein said rst component contains at least 3 organic rings. l

9. A light sensitive material for color photography comprising a support, a plurality of silver halide gelatine emulsions carried by said support, each emulsion containing an' organic colorless dyestui component capable of reacting with a further component to produce 'a dyestuff image diierent in color from that produced in the other layers, said rst component having a chemical constitution which imparts thereto substantive properties with respect to the gelatine.

10. A light-sensitive element as defined in claim 6, wherein said iirst component contains at least 3 organic rings, at least 2 of said rings being selected from th class of fused rings and rings connected together by a linkage selected from the class consisting of a direct nuclear carbon to nuclear carbon linkage, a -CH=N- linkage, a -NHCO- linkage, a -NH-CO-HN- linkage, a -NH--CS-NH- linkage, a CH2- NH- linkage and a -CH=CH- linkage.

11. A light-sensitive element as deiined in claim 6, wherein said rst component contains at least 3 organic rings, at least 2 of said rings being fused together.

12. A light sensitive element as defined in claim 6, wherein said iirst component contains at least 3 organic rings, at least one ring being heterocyclic.

13. A light-sensitive material for color photographycomprising a support and a silver halide gelatin emulsion thereon containing an hydroxynaphthoic acid arylide containing an organic group which imparts to said compound substantive character with respect to the gelatin.

colorless dyestui componentcapable of reacting with a further component to produce-a dyestuff image, said first component containing at least 3 organic rings, at least 2 of said rings beingselect ed from the class of fused rings `and rings vconnected together by a linkageselected from the group consisting of a direct lnuclear carbonio nuclear carbon linkage, a -CH==N- linkage, a

linkage and a -CI-I=CH-A linkage, said cornponents although being soluble `in aqueous solu` tions being fast to diffusion in the gelatim i JOHN EGGRTQ .ALFRED FROEHLICH. BRUNO WENDT.y

age, a -NH-cs-NH- linkage, a CH2- Nagin

Images