US3342592A - Photographic color films and processes - Google Patents

Photographic color films and processes Download PDF

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US3342592A
US3342592A US287746A US28774663A US3342592A US 3342592 A US3342592 A US 3342592A US 287746 A US287746 A US 287746A US 28774663 A US28774663 A US 28774663A US 3342592 A US3342592 A US 3342592A
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color
silver halide
sensitive
layer
layers
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Chu Victor Fu-Hua
Umberger Jacob Quentin
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32Colour coupling substances
    • G03C7/327Macromolecular coupling substances
    • G03C7/3275Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • a conventi-onal reversal element may comprise a support having coated thereon, in order, a red-sensitive, colloid silver halide emulsion layer which contains a cyan color coupler; a green-sensitive, colloid silver halide emulsion layer containing a magenta color coupler and a blue-sensitive, colloid silver halide emulsion layer containing a yellow color coupler.
  • All of the silver halide emulsion layers are conventionaly coated to give substantially the same coating weights based on the silver halide present in the emulsion.
  • the color couplers form the dyes in the respective layers by reacting with the oxidation products formed during development with aromatic amino color developing agents.
  • Auxiliary layers are also present such as a yellow filter layer between the blue-sensitive layer and the green-sensitive layer, antihalation layers, antiabrasion layers, etc.
  • This type of structure is defined as an integral system as compared to a non-integral system where the color couplers are incorporated in the processing solutions. It is the former type with which this invention is concerned.
  • the silver halide in the yellow layer must be completely color developed to give the maximum amount of oxidized color developer to react with the dye coupler.
  • the magenta and cyan layers become overdeveloped. This results in color contamination by virtue of the fact that excess oxidation products of the developer diffuse into adjacent layers where they react with color couplers to form dyes in nonimage areas where they are not wanted.
  • the non-integral system does seek to overcome these difiiculties by placing the: dye couplers in separate developing baths. This has the undesirable feature of relatively unstable developing solutions, and requires separate exposure of each of the respective layers and also separate development of each layer. This, of course, increases the complexity of the process or system.
  • a further object is to provide colored images of increased sharpness by a reversal development process.
  • a still further object is to provide colored images having fine grain, good color quality and improved sensitometric characteristics.
  • a still further object is to provide a color reversal system, the film element of which is easy to construct and the processing procedure of which is simple and easy to carry out.
  • the multilayer photographic color film of this invention comprises: (1) a transparent film bearing,
  • each silver halide layer is adapted to record light from a different primary color region, blue, green and red, of the visible spectrum and contains a non-ditlusing color former which upon chromogenic development of the exposed silver halide with a primary aromatic amino color developing agent forms a dye complementary in color to the utilized sensitivity of the emulsion layer;
  • said multilayer color film being characterized in that the outer blue-sensitive layer has a coat ing Weight not more than about /3 the silver halide coating weight of either of the green-sensitive and red-sensitive silver halide layers.
  • the structure of the preferred color reversal film of this invention comprises a support having coated thereon in order a colloidal silver antihalation layer, a red-sensitive gelatino silver iodobromide emulsion containing a cyan color coupler and an amount of about 25-40 milligrams of silver halide per square decimeter, a separator layer, a green-sensitive silver iodobromide emulsion containing 21 magenta color former and an amount of 2540 milligrams of silver halide per square decimeter, a yellow filter layer and a blue-sensitive silver iodobromide emulsion containing a yellow coupler and an amount of about 12-20 milligrams of silver bromide per square decimeter.
  • the element may also have a supercoat for antiabrasion purposes.
  • the cyan and magenta color couplers are present in their respective emulsions in a lower ratio based on silver halide than the yellow coupler.
  • the magenta and cyan couplers are present in a ratio of one mole of color coupler per six to twelve moles of silver halide and the yellow coupler is present in a ratio of one mole of color coupler to 2-4 moles of silver halide.
  • the amounts of magenta and cyan couplers usually may be varied over a wider range than the yellow color-former which should not be less than one mole of color-former to six moles of silver halide. All of the silver halide emulsions contain approximately one-half to twelve percent iodide on a molar basis.
  • the yellow dye density will be insufiicient for good color balance, or if the elementis color developed sufficiently to give the proper yellow dye density, the cyan and magenta will be over-developed. As described above, this results in an excess amount of oxidized developer which migrate to adjacent layers where it reacts with color coupler to give unwanted color contamination. It also results in a poor balance of contrasts for the three layers. The magenta and cyan gammas will be much higher than the gamma of the yellow layer which detracts from good color quality and reduces the exposure latitude of the film.
  • the film is exposed to a scene and developed in a black-and-white developer. After this step, the film is immersed in a shortstop bath and then washed. The film is then flashed by white light on both sides. This exposes the remaining silver halide in all of the layers. The film is then developed in a color developer to form colored images in the respective layers. The film is again bathed in a shortstop bath, washed and the developed silver removed by a bleach bath. The film is finally fixed and washed.
  • the process of thi -'nvention embodies a black-andwhite development of the original images, a second exposure and the color development stepis divided into two parts.
  • the blue-sensitive layer containing the yellow color coupler is exposed from the front, i.e., not through the support, to blue light and developed to, or nearly to, completion in a color developer which may or may not be, but preferably is, a high energy developer.
  • the greensensitive magenta color coupler-containing layer and the red-sensitive cyan color coupler-containinglayer are next exposed to white or yellow light and developed in the same or a different color developing composition, e.g., a low energy developer which may contain a competing coupling compound to complete the formation of colored images in all of the record layers.
  • This method assures that the maximum amount of silver halide is developed in the yellow layer and, of course, the formation of the maximum amount of yellow dye. It also assures that the magenta and cyan layers will not be overdeveloped but will be developed .to give the optimum desired characteristics of fine grain, color density and contrast.
  • the two-part development can be applied to the same type of film by first exposing the magenta and cyan layers to yellow light, partially developing these layers to give a low dye yield, e.g., in a developing bath containing a component which competes with the color'coupler for the developer oxidation products, then exposing the yellow layer to blue light and developing the element in a different bath to complete development of the magenta and cyan layers and to fully develop the yellow layer.
  • Example I To show the eifect of low silver halide coating weight on resolving power which is a measure of sharpness, a color reversal film was made in the following manner. On a cellulose ester support there was coated in order, a non-halation layer of the type disclosed in Firestine and Stevenson, U.S. Ser. No. 183,759, filed Mar.
  • the black-and-white developer had the following formula:
  • the shortstop bath had the following formula:
  • the color developer had the following formula:
  • Tetrasodium salt of ethylenediamine tetraacetic The bleach bath had the following formula:
  • Example 11 Acolor reversal film element was made as described in Example I with the bluesensitive yellow color coupler containing emulsion being coated to give a silver halide coating weight of 14 mg./dm. The green-sensitive magenta color coupler containing emulsion being coated to give a silver halide coating weight of 32 mg./dm. and the red-sensitive cyan color coupler containing emulsion being coated to give a silver halide coating weight of 33.5 mg./dm.
  • a second sample was processed in the following manner using a higher dye yield developer than for the first sample.
  • Example 111 Black-and-white developer minutes 10 Shortstop bath (see formula below) do 1 Wash do 2 White light exposure (G.E. Photo-DXC) 3 from film:
  • the color developer in the above process had the following formula:
  • the fixer composition had the following composition: Sodium thiosulfate (anhy.) grams 115 Sodium sulfite (anhy.) do 9 Water to make liter 1 pH 7.8+
  • Black-and-white developer (as in Example I) minutes 10 Shortstop bath do 1 Wash do 2 Blue exposure (Corning #5850) (3.5-4.5 mm. thickness) 10-watt incandescent lamp 3' from film) front seconds 16 Color Developer I (see formula below) minutes 15 3 Wash seconds 10 Shortstop bath "minutes” 2 Wash do 3 White light exposure (G.E. Photo-DXC) 3' from film:
  • each layer is well balanced as compared to more conventional processing as shown by the single color development processing by which the first sample was processed.
  • the Color Developer I above had the following formula: Tetrasodium salt of ethylenediamine tetraacetic acid grams 2 Sodium sulfide (anhy.) do 4 Potassium bromide do 0.5 Borax do 10 Sodium carbonate (monohydrate) do 10 Potassium iodide 0.1% sol ml 10 49 Sodium hydroxide 3 N ml 23 6-nitrobenzimidazole (0.5% EtOH sol.) rnl 2 p-Aminodiethylaniline grams 2.5 Water to make liter 1.0 pH 115:0.05
  • Example IV A sample of the color reversal film of Example III was exposed and processed in the following manner:
  • Example V Having fully established the fundamental principles on which to base the new film and process, steps were now taken to improve the invention and shorten development times for use in a continuous processing machine such as employed for processing 16 mm. and double-8 mm. color reversal motion pictures. Specifically, a film element was made as in Example I with the following detailed structural details.
  • the total emulsion thickness including the cyan, separator, magenta, filter, yellow and antiabrasion layers was measured to be 0.50 mil or 12.7 microns at normal conditions of temperature, 72 F., and relative humidity, 55%.
  • the film was slit to 16 mm. width and perforated for use as double-8 mm. film in a conventional 8 mm. motion picture camera. In such a way the film was exposed to a daylight outdoor scene at speed index equivalent to ASA 25. -It was then processed in a continuous processing machine (e.g., that manufactured by Andre Dbrie of France).
  • a continuous processing machine e.g., that manufactured by Andre Dbrie of France.
  • the color developing times were reduced to 10 min. and 4.5 min, respectively, for the first and second parts of the color development.
  • the film was slit to 8 mm. width as per normal practice.
  • the first color development after the frontal blue flash, is carried out under conditions to obtain maximum dye density in the yellow emulsion in which image graininess is not a problem due to the low visual opacity of the yellow dye.
  • This full development permits, as explained before, the use of a thin, low coating weight yellow emulsion for minimum scatter of the important magenta and cyan images.
  • the second development forms the visually opaque magenta and cyan dye images in which the grain structure of the dye deposits must -be fine for optimum definition, e.g., in 8 mm. projections.
  • the second color developer is formulated to yield lesser dye yields as can 'be attained via employment of competing couplers, e.g. sulfite ion or a soluble and migratory phenol such as citrazinic acid.
  • competing couplers e.g. sulfite ion or a soluble and migratory phenol such as citrazinic acid.
  • color-former is not a necessary limitation. Any of the non-diffusing color-formers known to be useful in gelatin layers of multilayer films can be used.
  • the useful color-formers are generally of high molecular weight, essentially colorless and contain as an active dye-forming or color-former nucleus, a structure of the formula:
  • nuclei are found in the reactive methylene dye intermediates and in aromatic hydroxyl compounds and includes the reactive ethenol groups. These groups occur in phenols, naphthols, acylacetamides, cyanoacetyls, beta-ketoesters, pyrazolones, homophthalimides, coumaranones, indoxyls, thioindoxyls, and inda- Z-olones.
  • Useful color-formers including those of this structure are described in U.S. Patents 2,758,029, 2,927,- 019, 2,927,024, 2,997,338, 3,070,442 in each of the patents listed therein and in the applications referred to above.
  • gelatino silver iodobromide emulsions are used, other silver halides and colloids besides gelatin may be used as the sole or additional binding agent for the silver halide grains, for example, various synthetic resins may be used.
  • emulsion additives as disclosed in assignees patent Jennings, US. 3,063,838, may be utilized.
  • the various auxiliary layers may be varied without disturbing the basic requirements as set forth above, namely a low coating weight yellow layer coupled with a two stage color development step.
  • inert ingredients e.g., pigments, colloidal silver, polymer latices, matting agents, etc. may be present in all of the element layers including the support.
  • a further advantage of the invention is that it provides new multicolor films and processes that permit full color development of the yellow layer Without over-development of the magenta and cyan layers.
  • the films and processes offer better sensitometric control of the total color element which is not now possible with the structures and processes of the prior art.
  • the elements and processes also ofler a simple and practical way of improving the image definition and color quality of the final color image. Still further advantages will be apparent to those skilled in the art of color photographic films and processes.
  • a color reversal process which comprises:
  • exposing imagewise to a multicolor scene a multilayer photographic color film comprising (1) a transparent film base bearing (2) three Water-permeable colloid-silver halide emulsion layers and (3) a yellow filter layer said layers so arranged and sensitized with the blue-sensitive layer outermost that each silver halide layer is adapted to record light from a different primary color region, blue, green and red, of the visible spectrum and contains a non-diffusing color-former which upon chromogenic development of the exposed silver halide with a primary aromatic amino color developing agent forms 45 a dye complementary in color to the utilized sensitivity of the emulsion layer; said multilayer color film being characterized in that the outer blue-sensitive layer has a coating weight not more than about of the silver halide coating weight of either of the green-sensitive and red-sensitive silver halide layers,
  • step (b) developing the original images formed in the multilayer color film during step (a) in a black-andwhite silver halide developer solution, then (i) exposing the developed element to blue light impinging first upon the outermost blue-sensitive layer and color-developing said layer substantially to completion in a high-energy silver halide developer solution containing a primary aromatic amino color-developing agent and a relatively low quantity of an alkali metal sulfite, and then (ii) exposing the green-sensitive and red-sensitive layers to white or yellow light, and developing the exposed green and red-sensitive layers in a low-energy silver halide developer solution containing a primary aromatic amino color-developing agent and a relatively high quantity of an alkali metal sulfite.
  • greensensitive and red-sensitive silver halide layers have approximately equal silver halide coating weights within the range of 25 to 40 milligrams per square decimeter.
  • magenta and cyan color-formers are present in the green-sensitive and red-sensitive layers, respectively, in the amount of 1 mole per 6 to 12 moles of silver halide, and the yellow color-former is present in the blue-sensitive layer in an amount of 1 mole per 2-6 moles of silver halide.

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Description

United States Patent 3,342,592 PHOTOGRAPHIC COLOR FILMS AND PROCESSES Victor Fu-Hua Chu, East Brunswick, and Jacob Quentin Umberger, Holmdel, N.J., assignors to E. I. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware N0 Drawing. Filed June 14, 1963, Ser. No. 287,746 4 Claims. (Cl. 96-22) This invention relates to color photography and more particularly to color reversal films and processes for forming multicolor images.
It is well known in the art to use multilayer reversal films for color photography. It is known further that the color couplers for such color reversal film elements may be incorporated in the separate emulsion layers or they may be incorporated in the developing baths. A conventi-onal reversal element may comprise a support having coated thereon, in order, a red-sensitive, colloid silver halide emulsion layer which contains a cyan color coupler; a green-sensitive, colloid silver halide emulsion layer containing a magenta color coupler and a blue-sensitive, colloid silver halide emulsion layer containing a yellow color coupler. All of the silver halide emulsion layers are conventionaly coated to give substantially the same coating weights based on the silver halide present in the emulsion. The color couplers form the dyes in the respective layers by reacting with the oxidation products formed during development with aromatic amino color developing agents. Auxiliary layers are also present such as a yellow filter layer between the blue-sensitive layer and the green-sensitive layer, antihalation layers, antiabrasion layers, etc. This type of structure is defined as an integral system as compared to a non-integral system where the color couplers are incorporated in the processing solutions. It is the former type with which this invention is concerned.
There are some serious drawbacks to the multilayer color reversal films used heretofore in color photographic processes. One of the most troublesome defects is poor image definition. This is due primarily to excessive lightscattering by the emulsion layers. Light scattering is, of course, a function of silver halide coating weight and grain size, and emulsion layer thickness. For obvious reasons, the red-sensitive cyan layer and green-sensitive magenta layer are conventionally placed below the outermost blue-sensitive emulsion layer and yellow filter layer. Therefore, it follows that light scattering increases from the outermost surface of the film toward the support. In other words, the thicker the layer and the greater the number of silver halide grains (coating weight) the greater Will be the amount of deflection and scattering of the light. It also becomes evident that the inner magenta and cyan layers which are the most important in contributing to image color quality are most affected by light scattering which is the chief detriment to image sharpness.
A further diificulty, which has been discovered is the effect caused by the low order of tinctorial strength of dyes formed from yellow dye couplers. That is to say, the tinctorial strength of the yellow dyes (molar extinction coeificient, e is 10,000 to 20,000) formed from yellow couplers now known has been found to be much lower than that of the magenta and cyan (e is 30,000 to 50,000). This compounds the problem of achieving a low light scattering yellow emulsion for improving the definition of the final color image. Much effort has been expended without success in searching for dye couplers which would give yellow dyes of higher tinctorial strength, particularly those attached to a polymer molecule by covalent bonding to make them non-migratory. In attempting to obtain the maximum amount of yellow dye, the silver halide in the yellow layer must be completely color developed to give the maximum amount of oxidized color developer to react with the dye coupler. However, by the time this is achieved during conventional processing, the magenta and cyan layers become overdeveloped. This results in color contamination by virtue of the fact that excess oxidation products of the developer diffuse into adjacent layers where they react with color couplers to form dyes in nonimage areas where they are not wanted.
The non-integral system, however, does seek to overcome these difiiculties by placing the: dye couplers in separate developing baths. This has the undesirable feature of relatively unstable developing solutions, and requires separate exposure of each of the respective layers and also separate development of each layer. This, of course, increases the complexity of the process or system.
It is therefore an object of this invention to provide a new element and process for producing color reversal images. A further object is to provide colored images of increased sharpness by a reversal development process. A still further object is to provide colored images having fine grain, good color quality and improved sensitometric characteristics. A still further object is to provide a color reversal system, the film element of which is easy to construct and the processing procedure of which is simple and easy to carry out.
The multilayer photographic color film of this invention comprises: (1) a transparent film bearing,
(2) three water-permeable colloid-silver halide emulsion layers, and (3) a yellow filter layer,
said layers so arranged and sensitized with the blue sensitive layer outermost that each silver halide layer is adapted to record light from a different primary color region, blue, green and red, of the visible spectrum and contains a non-ditlusing color former which upon chromogenic development of the exposed silver halide with a primary aromatic amino color developing agent forms a dye complementary in color to the utilized sensitivity of the emulsion layer; said multilayer color film being characterized in that the outer blue-sensitive layer has a coat ing Weight not more than about /3 the silver halide coating weight of either of the green-sensitive and red-sensitive silver halide layers.
The structure of the preferred color reversal film of this invention comprises a support having coated thereon in order a colloidal silver antihalation layer, a red-sensitive gelatino silver iodobromide emulsion containing a cyan color coupler and an amount of about 25-40 milligrams of silver halide per square decimeter, a separator layer, a green-sensitive silver iodobromide emulsion containing 21 magenta color former and an amount of 2540 milligrams of silver halide per square decimeter, a yellow filter layer and a blue-sensitive silver iodobromide emulsion containing a yellow coupler and an amount of about 12-20 milligrams of silver bromide per square decimeter. The element may also have a supercoat for antiabrasion purposes. The cyan and magenta color couplers are present in their respective emulsions in a lower ratio based on silver halide than the yellow coupler. Generally the magenta and cyan couplers are present in a ratio of one mole of color coupler per six to twelve moles of silver halide and the yellow coupler is present in a ratio of one mole of color coupler to 2-4 moles of silver halide. The amounts of magenta and cyan couplers usually may be varied over a wider range than the yellow color-former which should not be less than one mole of color-former to six moles of silver halide. All of the silver halide emulsions contain approximately one-half to twelve percent iodide on a molar basis.
If the novel multilayer color film just described is processed conventionally, the yellow dye density will be insufiicient for good color balance, or if the elementis color developed sufficiently to give the proper yellow dye density, the cyan and magenta will be over-developed. As described above, this results in an excess amount of oxidized developer which migrate to adjacent layers where it reacts with color coupler to give unwanted color contamination. It also results in a poor balance of contrasts for the three layers. The magenta and cyan gammas will be much higher than the gamma of the yellow layer which detracts from good color quality and reduces the exposure latitude of the film.
The above difiiculties are overcome in accordance with the process of this invention whereby a color image of excellent sharpness, fine grain and good color quality is obtained without the above processing difficulties. In conventional color processing, the film is exposed to a scene and developed in a black-and-white developer. After this step, the film is immersed in a shortstop bath and then washed. The film is then flashed by white light on both sides. This exposes the remaining silver halide in all of the layers. The film is then developed in a color developer to form colored images in the respective layers. The film is again bathed in a shortstop bath, washed and the developed silver removed by a bleach bath. The film is finally fixed and washed.
The process of thi -'nvention embodies a black-andwhite development of the original images, a second exposure and the color development stepis divided into two parts. The blue-sensitive layer containing the yellow color coupler is exposed from the front, i.e., not through the support, to blue light and developed to, or nearly to, completion in a color developer which may or may not be, but preferably is, a high energy developer. The greensensitive magenta color coupler-containing layer and the red-sensitive cyan color coupler-containinglayer are next exposed to white or yellow light and developed in the same or a different color developing composition, e.g., a low energy developer which may contain a competing coupling compound to complete the formation of colored images in all of the record layers. This method assures that the maximum amount of silver halide is developed in the yellow layer and, of course, the formation of the maximum amount of yellow dye. It also assures that the magenta and cyan layers will not be overdeveloped but will be developed .to give the optimum desired characteristics of fine grain, color density and contrast.
The two-part development can be applied to the same type of film by first exposing the magenta and cyan layers to yellow light, partially developing these layers to give a low dye yield, e.g., in a developing bath containing a component which competes with the color'coupler for the developer oxidation products, then exposing the yellow layer to blue light and developing the element in a different bath to complete development of the magenta and cyan layers and to fully develop the yellow layer.
The invention will now be illustrated by, but is not intended to be limited to the following examples.
Example I To show the eifect of low silver halide coating weight on resolving power which is a measure of sharpness, a color reversal film was made in the following manner. On a cellulose ester support there was coated in order, a non-halation layer of the type disclosed in Firestine and Stevenson, U.S. Ser. No. 183,759, filed Mar. 30, 1962, now abandoned, a red-sensitive gelatino silver iodobromide layer containing the cyan color-former in a ratio of one mole color-former to eight moles ilver halide, a gelatin separator layer, a green-sensitive gelatino silver iodobromide layer containing a magenta color-former in a ratio of one mole color-former to eight moles of silver halide, a gelatin yellow colloidal silver filter layer and finally a blue-sensitive gelatino silver'iodobromide layer containing a yellow color-former in a ratioof one mole color-former to four moles of silver halide. All of the emulsion layers were coated to a silver halide coating weight of about 33.5 mg./dm. At the same time, a similar three layer element was coated with the exception that the blue-sensitive layer was coated to give a silver halide coating weight of about 17.7 rng/dm. having the same emulsion layer thickness as that of the heavier emulsions above. The yellow color-former was that disclosed in Mc- Queen US 2,513,190, June 27, 1950, the cyan colorformer was made according to Example I of Umberger U.S. Ser. No. 113,101, filed May 29, 1961, now aban cloned, and the magenta color-former was made according to Firestine et al. US. Ser. No. 21,959, filed Apr. 13, 1960, US. Patent 3,163,625, Dec. 29, 1964. The cited applications are owned by the assignee of this application.
The resulting color elements were given l-second exposures on the Resolvometer described in Science and Ape plications of Photography, Proceedings of the R.P.S. Centenary Conference, London, 1953, Grossman, pp. 292 297. The exposed element was then processed according to the following procedure:
Temperature F 75 Black-and-white developer minutes 10 Shortstop bath do 2 Wash in water do 2 White light exposure (GE. Photo-DXC):
Front seconds 15 Back do 15 Color developer minutes 15 Wash in water seconds 10 Shortstop bath minutes 2 Wash in water do 3 Bleach do 6 Wash in water do 2 Fix do 3 Wash in water do 8 Dry.
The black-and-white developer had the following formula:
N-methylaminophenol hydrosulfate grams 3 Hydroquinone do 10 Sodium sulfite (anhyd) do Sodium carbonate (monohydrate) do 50 Potassium bromide L do 5 Potassium iodide (0.1% solution) ml 10 Vitreous sodium phosphate grams 2 Water to make liter 1 pH at 75 F. L 10.0 -.05
The shortstop bath had the following formula:
Chrome alum grams 15.0 Acetic acid, glacial ml 6.5 Water to make liter 1.0
The color developer had the following formula:
Tetrasodium salt of ethylenediamine tetraacetic The bleach bath had the following formula:
results:
Viewiu g Light Blue Green Red White Control (all layers having approxi mately equal coating weights) 91 77 67 77 Color film with yellow layer at 17.7
Lug/din. 115 100 83 93 It will be seen that there is a significant improvement in resolving power for each of the three viewing filters and for the colored image as a whole. This, of course, indicates a substantial improvement in image sharpness, which is a function of resolving power, but this film was deficient in yellow developed dye. The control film had adequate yellow image density but had less than optimum definition.
Example 11 Acolor reversal film element was made as described in Example I with the bluesensitive yellow color coupler containing emulsion being coated to give a silver halide coating weight of 14 mg./dm. The green-sensitive magenta color coupler containing emulsion being coated to give a silver halide coating weight of 32 mg./dm. and the red-sensitive cyan color coupler containing emulsion being coated to give a silver halide coating weight of 33.5 mg./dm.
One sample of the resulting color film was exposed in an intensity scale sensitometer according to ASA- PH2.11 procedure and processed in the following manner:
Black and white development as in Example The maximum densities, average contrasts, and gammas of the yellow, magenta and cyan layers were as follows:
Yellow Magenta Cyan D-max 1.61 3.82 3. 45 Av. Contrast low 2. 46 2. 31 Gamma 1.16 3.27 3.30
A second sample was processed in the following manner using a higher dye yield developer than for the first sample.
Black-and-white developer as above minutes 10 Shortstop do 1 Wash do 1 Blue ligat QLBEBQ EEHEHQ 555573.5 1; mm. thickness) 10-w. incandescent lamp at 3 ft., front seconds 16 Color development (see Color Developer II below) minutes 22 Wash seconds 10 Shortstop bath minutes 2 Wash do 3 White light exposure (G.E. Photo-DXC) 3 from film:
Front seconds 15 Back do 15 Color development (see Color Developer II below) minutes 8 Wash seconds 10 Shortstop bath minutes 2 Wash do 3 Bleach do 6 Wash do 2 Fix do 3 Wash do 8 Upon drying, the maximum average contrasts, gammas, and densities of the yellow, magenta and cyan layers A comparison of the above densities with those obtained with the first sample shows quite clearly that the D- max. of the yellow layer has been increased from 1.61 to 3.41 and approximates the values of the maximum densities of the magenta and cyan layers. It will also be seen that average contrasts and gamma of the yellow image match the corresponding magenta and cyan values very well. This of course, results in greatly improved color quality in the color prints when the above color element is used in practice and processed in the above manner.
The formula for Color Developer I that is referred to The formula for the Color Developer II in the above process is as follows:
Water ml 800 Tetrasodium salt of ethylenediamine tetraacetic acid grams 2 Sodium sulfite (anhy.) 'do 4 Potassium bromide do 0.5 Borax do 10 Sodium carbonate (monohydrate) do 10 Potassium iodide 0.1% aqueous solution ml 10 Sodium hydroxide 3 N ml 24 p-Aminodiethylaniline grams 2.5
7 Polyethylene glycol (mol wt. 30003700) do 2 6-nitrobenzimidazole (0.5% EtOH sol.) ml 2 Water to make liter 1.0 pH 115-0.05
Example 111 Black-and-white developer minutes 10 Shortstop bath (see formula below) do 1 Wash do 2 White light exposure (G.E. Photo-DXC) 3 from film:
Front seconds 15 Back do 15 Color developer (see formula below) minutes 12 Wash seconds 10 Shortstop bath "minutes" 2 Wash do 3 Bleach do 6 Wash do 2 Fixer (see formula below) do 3 Wash do 8 The sensitometric characteristics were as follows:
Yellow Magenta Cyan D-max 1.53 3.55 3.24 Av Oontrast low 2. 65 2.06 Gamma 1. 24 3. 28 2. 56
The color developer in the above process had the following formula:
Tetrasodium salt of ethylenediamine tetraacetic acid grams 2.0 Sodium sulfite (anhy.) do 20.0 Potassium bromide do 0.5 Borax do 10.0 Sodium carbonate (mono) do 10.0 Potassium iodide 0.1% sol. ml 10.0 Sodium hydroxide 3 N ml 24.0 p-Aminodiethylaniline grams 2.5 Water to make liter 1.0 pH at 75 F. 115-3005 The shortstop bath had the following composition: Water ml 970.0 Potassium chrome alum grams 30.0 Sulfuric acid 3 N ml 3.3 Water to make 1iter 1.0 pI-I 2.50:.05
The fixer composition had the following composition: Sodium thiosulfate (anhy.) grams 115 Sodium sulfite (anhy.) do 9 Water to make liter 1 pH 7.8+
A second sample of the above film was processed as follows:
Black-and-white developer (as in Example I) minutes 10 Shortstop bath do 1 Wash do 2 Blue exposure (Corning #5850) (3.5-4.5 mm. thickness) 10-watt incandescent lamp 3' from film) front seconds 16 Color Developer I (see formula below) minutes 15 3 Wash seconds 10 Shortstop bath "minutes" 2 Wash do 3 White light exposure (G.E. Photo-DXC) 3' from film:
Front seconds 15 Back do 15 Color Developer II minutes 18 Wash seconds 10 Shortstop bath minutes 2 Wash do 3 Bleach do 6 Wash do 2 Fix (see formula above) do 3 Wash do 8 The sensitometric characteristics were as follows:
20 Yellow Magenta Cyan D-max k 2. 98 3.09 2. 94 Av. Contrast -2 2.03 2.24 1.87 Gamma 2. 50 2. 54 2. 56
It will be seen that the characteristics of each layer are well balanced as compared to more conventional processing as shown by the single color development processing by which the first sample was processed.
The Color Developer I above had the following formula: Tetrasodium salt of ethylenediamine tetraacetic acid grams 2 Sodium sulfide (anhy.) do 4 Potassium bromide do 0.5 Borax do 10 Sodium carbonate (monohydrate) do 10 Potassium iodide 0.1% sol ml 10 49 Sodium hydroxide 3 N ml 23 6-nitrobenzimidazole (0.5% EtOH sol.) rnl 2 p-Aminodiethylaniline grams 2.5 Water to make liter 1.0 pH 115:0.05
The Color Developer II above had the following formula:
Water ml 800 Tetrasodium salt of ethylenediamine tetraacetic acid grams 2 Sodium sulfite (anhy.) do 20 Potassium bromide do 0.5 Borax do 10 Sodium carbonate do 10 Potassium iodide 0.1% sol. ml 10 Sodium hydroxide 3 N ml 20 p-Aminodiethylaniline grams 1.5 Water to make liter 1 pH adjusted to 11.5 L0.05
Example IV A sample of the color reversal film of Example III was exposed and processed in the following manner:
Black-and-white developer minutes 10 Shortstop bath do 1 Wash do 2 Blue light exposure (Corning #5850 (3.54.5 mm. thickness) 10-watt incandescent 3' from film), front seconds 16 Color developer (see Color Developer I of Example III) minutes 18 Wash seconds 10 Shortstop bath minutes 2 Wash do 3 9 White light exposure (G.E. Photo-DXC) 3' from film:
Front seccmd= 15 Back do 15 Color developer (see formula below) minutes Wash seconds 10 Shortstop bath minutes 2 Wash do-.. 3 Bleach do 6 Wash do.. 2 Fix do 3 Wash do 8 The sensitometric results are as follows:
Yellow Magenta Cyan As compared to the control in Example III, it will be seen that the yellow layer characteristics are much improved and more closely match those of the magenta and cyan layers.
1 The formula for the second color developer is as follows:
Example V Having fully established the fundamental principles on which to base the new film and process, steps were now taken to improve the invention and shorten development times for use in a continuous processing machine such as employed for processing 16 mm. and double-8 mm. color reversal motion pictures. Specifically, a film element was made as in Example I with the following detailed structural details.
Layer AgBr Ctg. Wgt., AgBrzColor Former mg. /d1u. 2 Ratio (M oles M oles) Yellow Emulsion 15. 9 4:1 Magenta Emulsion 29.0 9:1 Cyan Emulsion 27.1 8:1
The total emulsion thickness including the cyan, separator, magenta, filter, yellow and antiabrasion layers was measured to be 0.50 mil or 12.7 microns at normal conditions of temperature, 72 F., and relative humidity, 55%.
The film was slit to 16 mm. width and perforated for use as double-8 mm. film in a conventional 8 mm. motion picture camera. In such a way the film was exposed to a daylight outdoor scene at speed index equivalent to ASA 25. -It was then processed in a continuous processing machine (e.g., that manufactured by Andre Dbrie of France). By use of increased agitation of the developing solutions of Example III and increasing the concentration of p-aminodiethylaniline in the Color Developer I from 2.5 gals/liter to 5.0 gms./liter and adding 2.0 gms./liter of polyethylene glycol of mol. wgt. 3000-7000, the color developing times were reduced to 10 min. and 4.5 min, respectively, for the first and second parts of the color development. Following the processing, the film was slit to 8 mm. width as per normal practice.
On projection the 8 mm. color motion pictures were found to have higher image definition and less graininess when compared with'8 mm. film of the non-integral coupler type and with color films of the integral type but with structures having equivalent silver halide coating weights in all layers and processed with a single color development step. It was found that still further shortening of the processing times was achievable by raising all processing solution temperatures by 5 F. to achieve F. processing which is standard for many commercial films.
From the examples it is clear that the first color development, after the frontal blue flash, is carried out under conditions to obtain maximum dye density in the yellow emulsion in which image graininess is not a problem due to the low visual opacity of the yellow dye. This full development permits, as explained before, the use of a thin, low coating weight yellow emulsion for minimum scatter of the important magenta and cyan images. In contrast with the first color developer for the yellow dye formation, the second development forms the visually opaque magenta and cyan dye images in which the grain structure of the dye deposits must -be fine for optimum definition, e.g., in 8 mm. projections.
Accordingly the second color developer is formulated to yield lesser dye yields as can 'be attained via employment of competing couplers, e.g. sulfite ion or a soluble and migratory phenol such as citrazinic acid. This is in accord with the well-known principle that any process which intensifies the developed image also increases the image graininess. For a discussion of the relative contribntions to graininess and definition of typical yellow, magenta, and cyan dyes see the article in Phot. Sci. and Eng, 7, page 36 (1963) by J. Q. Umberger.
While the invention is directed to color reversal multilayer elements containing certain color couplers, it is obvious that the particular type of color-former is not a necessary limitation. Any of the non-diffusing color-formers known to be useful in gelatin layers of multilayer films can be used. The useful color-formers are generally of high molecular weight, essentially colorless and contain as an active dye-forming or color-former nucleus, a structure of the formula:
which is a general structure of the color-coupling nucleus in an enol form.
The foregoing nuclei are found in the reactive methylene dye intermediates and in aromatic hydroxyl compounds and includes the reactive ethenol groups. These groups occur in phenols, naphthols, acylacetamides, cyanoacetyls, beta-ketoesters, pyrazolones, homophthalimides, coumaranones, indoxyls, thioindoxyls, and inda- Z-olones. Useful color-formers including those of this structure are described in U.S. Patents 2,758,029, 2,927,- 019, 2,927,024, 2,997,338, 3,070,442 in each of the patents listed therein and in the applications referred to above.
Likewise although gelatino silver iodobromide emulsions are used, other silver halides and colloids besides gelatin may be used as the sole or additional binding agent for the silver halide grains, for example, various synthetic resins may be used. Also, emulsion additives as disclosed in assignees patent Jennings, US. 3,063,838, may be utilized. The various auxiliary layers may be varied without disturbing the basic requirements as set forth above, namely a low coating weight yellow layer coupled with a two stage color development step. For example, inert ingredients, e.g., pigments, colloidal silver, polymer latices, matting agents, etc. may be present in all of the element layers including the support. In addition to cellulosic supports, of course other synthetic resins which have been described in the art as suitable for photographic supports may be used. For example, the supports disclosed and claimed in Alles and Saner, US. 2,627,088, dated Feb. 3, 1953 may be used.
It has been found that a high ratio of color-former to silver halide produces large image intensification suitable for use in a low silver halide coating weight yellow emulsion. It has also been found that a low ratio of colorformer to silver halide produces dye images of fine image texture 'or grain suitable for use in the visually opaque magenta and cyan emulsions. Thus, the above combination of high color-former to silver halide in the yellow and low color former to silver halide in the magenta and cyan optimizes the conditions for maximum image definition and color quality and constitute advantages of this invention.
A further advantage of the invention is that it provides new multicolor films and processes that permit full color development of the yellow layer Without over-development of the magenta and cyan layers. The films and processes offer better sensitometric control of the total color element which is not now possible with the structures and processes of the prior art. The elements and processes also ofler a simple and practical way of improving the image definition and color quality of the final color image. Still further advantages will be apparent to those skilled in the art of color photographic films and processes.
What is claimed is:
1. A color reversal process which comprises:
(a) exposing imagewise to a multicolor scene a multilayer photographic color film comprising (1) a transparent film base bearing (2) three Water-permeable colloid-silver halide emulsion layers and (3) a yellow filter layer said layers so arranged and sensitized with the blue-sensitive layer outermost that each silver halide layer is adapted to record light from a different primary color region, blue, green and red, of the visible spectrum and contains a non-diffusing color-former which upon chromogenic development of the exposed silver halide with a primary aromatic amino color developing agent forms 45 a dye complementary in color to the utilized sensitivity of the emulsion layer; said multilayer color film being characterized in that the outer blue-sensitive layer has a coating weight not more than about of the silver halide coating weight of either of the green-sensitive and red-sensitive silver halide layers,
5 (b) developing the original images formed in the multilayer color film during step (a) in a black-andwhite silver halide developer solution, then (i) exposing the developed element to blue light impinging first upon the outermost blue-sensitive layer and color-developing said layer substantially to completion in a high-energy silver halide developer solution containing a primary aromatic amino color-developing agent and a relatively low quantity of an alkali metal sulfite, and then (ii) exposing the green-sensitive and red-sensitive layers to white or yellow light, and developing the exposed green and red-sensitive layers in a low-energy silver halide developer solution containing a primary aromatic amino color-developing agent and a relatively high quantity of an alkali metal sulfite.
2. A process as set forth in claim 1 wherein the greensensitive and red-sensitive silver halide layers have approximately equal silver halide coating weights within the range of 25 to 40 milligrams per square decimeter.
3. A process as set forth in claim 1 wherein said film has an antihalation layer between the transparent support and the appertaining silver halide emulsion layer.
4. A process according to claim 1 wherein magenta and cyan color-formers are present in the green-sensitive and red-sensitive layers, respectively, in the amount of 1 mole per 6 to 12 moles of silver halide, and the yellow color-former is present in the blue-sensitive layer in an amount of 1 mole per 2-6 moles of silver halide.
References Cited UNITED STATES PATENTS 1,900,870 3/1933 Seymour 96-22 2,252,718 8/1941 Mannes et al. 96.22 3,211,552 10/1965 Chu et al. 96-22 OTHER REFERENCES Behrendt: Photo-Technik and Wirtschaft, vol. 10, pp. 194-498 (1959).
J. TRAVIS BROWN, Primary Examiner.

Claims (1)

1. A COLOR REVERSAL PROCESS WHICH COMPRISES: (A) EXPOSING IMAGWISE TO A MULTICOLOR SCENE A MULTILAYER PHOTOGRAPHIC COLOR FILM COMPRISING (1) A TRANSPARENT FILM BASE BEARING (2) THREE WATER-PERMEABLE COLLOID-SILVER HALIDE EMULSION LAYERS AND (3) A YELLOW FILTER LAYER SAID LAYERS SO ARRANGED AND SENSITIZED WITH THE BLUE-SENSITIVE LAYER OUTERMOST THAT EACH SILVER HALIDE LAYER IS ADAPTED TO RECORD LIGHT FROM A DIFFERENT PRIMARY COLOR REGION, BLUE, GREEN AND RED, OF THE VISIBLE SPECTRUM AND CONTAINS A NON-DIFFUSING COLOR-FORMER WHICH UPON CHROMOGENIC DEVELOPMENT OF THE EXPOSED SILVER HALIDE WITH A PRIMARY AROMATIC AMINO COLOR DEVELOPING AGENT FORMS A DYE COMPLEMENTARY IN COLOR TO THE UTILIZED SENSITIVITY OF THE EMULSION LAYER; SAID MULTILAYER COLOR FILM BEING CHARACTERIZED IN THAT THE OUTER BLUE-SENSITIVE LAYER HAS A COATING WEIGHT NOT MORE THAN ABOUT 2/3 OF THE SILVER HALIDE COATING WEIGHT OF EITHER OF THE GREEN-SENSITIVE AND RED-SENSITIVE SILVER HALIDE LAYERS, (B) DEVELOPING THE ORIGINAL IMAGES FORMED IN THE MULTILAYER COLOR FILM DURING STEP (A) IN A BLACK-ANDWHITE SILVER HALIDE DEVELOPER SOLUTION, THEN (I) EXPOSING THE DEVELOPED ELEMENT TO BLUE LIGHT IMPINGING FIRST UPON THE OUTERMOST BLUE-SENSITIVE LAYER AND COLOR-DEVELOPING SAID LAYER SUBSTANTIALLY TO COMPLETION IN A HIGH-ENERGY SILVER HALIDE DEVELOPER SOLUTION CONTAINING A PRIMARY AROMATIC AMINO COLOR-DEVELOPING AGENT AND A RELATIVELY LOW QUANTITY OF AN ALKALI METAL SULFITE, AND THEN (II) EXPOSING THE GREEN-SENSITIVE AND RED-SENSITIVE LAYERS TO WHITE OR YELLOW LIGHT, AND DEVELOPING THE EXPOSED GREEN- AND RED-SENSITIVE LAYERS IN A LOW-ENERGY SILVER HALIDE DEVELOPER SOLUTION CONTAINING A PRIMARY AROMATIC AMINO COLOR-DEVELOPING AGENT AND A RELATIVELY HIGH QUANTITY OF AN ALKALI METAL SULFITE.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219615A (en) * 1975-06-12 1980-08-26 Fuji Photo Film Co., Ltd. Color intensification process for sound images
EP0268150A2 (en) * 1986-11-15 1988-05-25 Konica Corporation Silver halide color photographic light-sensitive material
EP0277647A2 (en) * 1987-02-05 1988-08-10 Konica Corporation Silver halide light-sensitive color photographic material improved on the sharpness and graininess thereof
EP0283242A2 (en) * 1987-03-17 1988-09-21 Konica Corporation Silver halide colour photographic light-sensitive material
EP0306246A2 (en) * 1987-08-31 1989-03-08 Konica Corporation Silver halide photographic material
EP0323215A2 (en) * 1987-12-28 1989-07-05 Konica Corporation Photosensitive silver halide photographic material
USH1127H (en) 1987-08-31 1993-01-05 Konica Corporation Silver halide photographic material
US5340710A (en) * 1987-12-28 1994-08-23 Konica Corporation Photosensitive silver halide photographic material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1900870A (en) * 1932-04-26 1933-03-07 Eastman Kodak Co Photographic color process
US2252718A (en) * 1937-11-19 1941-08-19 Eastman Kodak Co Reversal process of color photography
US3211552A (en) * 1961-05-29 1965-10-12 Du Pont Multilayer photographic element for color photography

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD6548A (en) *

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1900870A (en) * 1932-04-26 1933-03-07 Eastman Kodak Co Photographic color process
US2252718A (en) * 1937-11-19 1941-08-19 Eastman Kodak Co Reversal process of color photography
US3211552A (en) * 1961-05-29 1965-10-12 Du Pont Multilayer photographic element for color photography

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219615A (en) * 1975-06-12 1980-08-26 Fuji Photo Film Co., Ltd. Color intensification process for sound images
EP0268150A3 (en) * 1986-11-15 1989-07-12 Konica Corporation Silver halide color photographic light-sensitive material
EP0268150A2 (en) * 1986-11-15 1988-05-25 Konica Corporation Silver halide color photographic light-sensitive material
EP0277647A2 (en) * 1987-02-05 1988-08-10 Konica Corporation Silver halide light-sensitive color photographic material improved on the sharpness and graininess thereof
EP0277647A3 (en) * 1987-02-05 1989-09-06 Konica Corporation Silver halide light-sensitive color photographic material improved on the sharpness and graininess thereof
EP0283242A2 (en) * 1987-03-17 1988-09-21 Konica Corporation Silver halide colour photographic light-sensitive material
EP0283242A3 (en) * 1987-03-17 1989-09-06 Konica Corporation Silver halide colour photographic light-sensitive material
US5009988A (en) * 1987-03-17 1991-04-23 Konica Corporation Silver halide color photographic light-sensitive material
EP0306246A2 (en) * 1987-08-31 1989-03-08 Konica Corporation Silver halide photographic material
EP0306246A3 (en) * 1987-08-31 1990-03-07 Konica Corporation Silver halide photographic material
USH1127H (en) 1987-08-31 1993-01-05 Konica Corporation Silver halide photographic material
EP0323215A2 (en) * 1987-12-28 1989-07-05 Konica Corporation Photosensitive silver halide photographic material
EP0323215A3 (en) * 1987-12-28 1990-08-22 Konica Corporation Photosensitive silver halide photographic material
US5340710A (en) * 1987-12-28 1994-08-23 Konica Corporation Photosensitive silver halide photographic material

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