US2742832A - Controlling grain and contrast in color photography - Google Patents

Controlling grain and contrast in color photography Download PDF

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Publication number
US2742832A
US2742832A US488957A US48895755A US2742832A US 2742832 A US2742832 A US 2742832A US 488957 A US488957 A US 488957A US 48895755 A US48895755 A US 48895755A US 2742832 A US2742832 A US 2742832A
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United States
Prior art keywords
color
coupler
image
competing
silver halide
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Expired - Lifetime
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US488957A
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English (en)
Inventor
Salminen Ilmari
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE545183D priority Critical patent/BE545183A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US488957A priority patent/US2742832A/en
Priority to GB384/56A priority patent/GB784479A/en
Priority to FR1149695D priority patent/FR1149695A/fr
Priority to DEE11960A priority patent/DE1002198B/de
Application granted granted Critical
Publication of US2742832A publication Critical patent/US2742832A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances

Definitions

  • the added agent competes with the coupler for the oxidized developer and thereby permits the formation during color development of an amount of oxidized developer in excess of that required to produce dye images of normal contrast. 7
  • This permits the use of larger amounts of silver halide in the emulsion layers, and. as the end result one obtains dye images of the desired normal contrast which do not have the exaggerated graininess and low sharpness and definition which characterizethe images produced by conven tional color development procedures.
  • One object of my invention is to'provide a process for obtaining dye images with improved graininess and sharpness characteristics.
  • a further object is to provide a method for obtaining dye images of normal contrast by color development of silver halide emulsion layers which contain amounts of silver halide in excess of that required for the production of dye images by conventional color development procedures.
  • Another object of the invention resides in repressing theinterimage effects which result from the wandering of oxidized developer, for example, from one layer to another in multilayer color film.
  • the objects of my invention are preferably accomplished by using, for the formation of colored photographic images, silver halide emulsion layers containing amounts of silver halide in excess of those required'to produce images of normal contrast when conventional color development is carried out, and conductingthe color development of such emulsion layer in the presence of a compound, referred to hereinafter as a competing coupler, which competes with'another coupler present for the oxidized developer.
  • the competing couplers appear to react with the oxidized developing agent to produce a Color development processes utilizing color ,development as the means of dye image formation are conven- 'iently divided into two classifications, which difier in the method of introducing the couplers into the system.
  • the first type of such processes makes use of couplers which are soluble in the color developer solution and which are Here the dye-forming reactions occur between two components of the color developer solution to produce a dye which is nondiffusible.
  • the second type of'color processes non-ditfusing image-forming couplers are incorporated in the silver halide emulsion layers and the coupling reactions occur between these incorporated couplers and the primary aromatic amino developing agent supplied from the color developer solution as shown in Mannes et al. U. S. Patent 2,304,940 and Jelley and Vittum U. S. Patent 2,322,027.
  • My invention is applicable to both types of color processes.
  • the color developer solution contains ,the color developing agent,,the dye-image-forming coupler, and'the competing coupler.
  • the developer solution contains the color developing agent and the competing cou- 3 pler, or alternatively, the competing coupler can also be incorporated in the silver Halide emulsion layers.
  • competing coupler is meant one which can be incorporated in the developer or emulsion layer and which forms a soluble dye which quickly diffuses out of the emulsion layer
  • image-forming coupler is meant one which can be incorporated in the developer or emulsion layer, but forms a comparatively permanent, non-ditfusing dye.
  • the competing coupler compounds of the present inventibn have a lower reactivity than the mentioned sulfonated coupler compounds, they can be used in higher concentrations in the developer solution and consequently the local exhaustion efiects are minimized.
  • the reactivity of the competing coupler compounds of my invention is sutficiently high that excessively large concentrations are not required to give the desired degree of contrast reduction.
  • the competing couplers which areemployed in my invention in conjunction with image-forming couplers are 3,5-dihydroxybenzoic acid, 2,6-dihydroxyisonicotinic acid, and derivatives of these compounds having the general formula:
  • R represents a member of the class consisting "of hydroxyl, alkoxyl groups, e. g. methoxyl, ethoxyl,
  • sisting of a hydrogen atom and an acyl group of an organicacid e. g. acetyland lauroyl
  • Xand Y represent the carbon atoms necessary to complete a 6-membered ring
  • the competing couplers having this formula have a nuclear position capable of coupling with the oxidation product of a primary aromatic amino silver halide developing agent produced in color development processes.
  • a multilayer color film having coated on a film base a red-sensitized silver halide emulsion layer having dispersed therein the cyan-forming coupler compound, 2-(diamylphenoxyacetamido) 4,6 dichloro 5- methylphenol. Over this emulsion layer is coated a thin gelatin layer, and then a green-sensitized emulsion layer containing a dispersion of the magenta-forming coupler compound, 1-(2',4',6'trichloropheny1)-3-[3"(2,4"'-diamylphenoxyacetamido)benzanfidol-S-pyrazolone.
  • curves (3, M and Y show the contrast of the cyan, magenta and yellow dye images developed as described in the absence of the competing coupler compound, and in general such contrasts are higher than desired.
  • Curves Ca, Ma and Ya show the lower contrasts of the cyan, magenta and yellow dye images obtained through development in the presence of the competing coupler compound. Itis apparent therefrom that the employment of the competing coupler compound in the development of the emulsion layers rich in silver halide has lowered the contrast of the dye images to the desired contrast of the process.
  • the competing couplers of the invention may also be incorporated into one or more of Exa mple II
  • the use of a competing coupler compound in a mixed grain or packet emulsion system of color photography is illustrated as follows:
  • a single-layer, two-color mixed packet coating capable of development to produce cyan and magenta images was prepared on film base, using the method described in U. S. Patent 2,698,794, granted January 4, 1955.
  • each of the strips was placed in a color developer solution containing 2-methyl-4-diethylamino aniline as the color developing agent, one of the color developer solutions containing no competing coupler and the other containing 10grams per liter of 2,6-dihydroxyisonicotinic acid as the competing coupler.
  • the time of color development was 10' minutes for both strips.- Following the color development, the two strips were put through the remainder of the processing cycle together, as follows:
  • the more soluble competing coupler compounds of the invention such as compoundsNos. 1 to 4, 9, 10, 13 to 15 and 19 are preferably incorporated intoemulsions such as illustrated in Examples Land I]. above as their alkali metal salts. All of the coupler compounds may however be dispersed in such emulsion layers by means of oily coupler solvents by means ot the methods of the above patents.
  • the esterified competing couplers illustrated above when used in emulsions can be expected to hydrolyze during the development process. to yield eventually the soluble dyes capable of being Washed out- 'i A comparison of the activity. of representatives competing couplers of the invention was carried out in the following manner.
  • a fast bromo-iodide film was provided by the methods of the above patents having dis-- persed in the emulsion layer the cyan forming coupler compound Z-(diamylphenoxyacetamido)-4,6 dichloro-S- methyl phenol.
  • a sample of the film was exposed under an image having graduated density and developed in a conventional color developer free of coupler compounds such as shown in the-above patents, followed by removal of the silver image and fixation. The density values of the silver image obtained as well as the density values of the dye image were noted.
  • Couplers of the invention are employed in color developing compositions also containing image-forming couplers or when employed in emulsion layers also containing imageforming coupler compounds, as well as when the emulsions contain the competing coupler compounds of the invention and the image-forming coupler compounds are present in the color developing solution.
  • My process is primarily designed for, although not limited to use in systems of color photography employing superposed emulsion layers sensitized to the primary regions of the visible spectrum and containing in the respective emulsion layers nonditfusing image-forming coupler compounds yielding differently colored dye images.
  • my invention is employed as described with these superimposed emulsion layers and development is carried out in a color-forming developer composition containing a competing coupler yielding a diffusible dye, the contrast and grain characteristics of the dye images in all emulsion layers are improved substantially.
  • the contrast reduction is illustrated in the drawings.
  • Such films may be utilized in the well-known negative-positive and reversal color development processes in the manner described in the above examples.
  • the silver halide concentration per unit areas of the emulsion layers employed in my invention is that necessary to reduce the contrast and grain to the desired value and can be varied within rather wide limits depending upon the result desired and the particular process which is under consideration.
  • Substantial improvements in grain characteristics are obtained by using at least about 50 milligrams per square foot of emulsion and preferably about 2 to 25 times the usual silver halide concentration of incorporated coupler'proccsses, or from about 50 to 750 milligrams of' silver halide (calculated as silver) per square foot of emulsion.
  • the emulsions '8 contain substantially more than about 50 milligrams of silver per square foot, normal color development in absence of diffusible coupler compounds yields greater con trast than usually desired in color processes.
  • the quantity of competing diffusible coupler which is used in the color developing compositions is dependent upon a number of factors. One of these is the relative coupling activity of the image-forming couplers compared to that of the competing couplers. In a given color system a suitable type and quantity of competing coupler can be readily ascertained. Another factor is the contrast desired in the particular color process under consideration. That is, in a color printing process a contrast of 2.5 may be desired, whereas in a negative color process, a contrast of only about 0.7 may be desired. More competing diffusible coupler can be employed in conjunction with the latter process to effect a greater reduction in contrast.
  • these color films may contain in the respective emulsion layers nondiffusible imageforming couplers of different coupler activity. Therefore, the relative increase in the silver halide concentration required in the emulsion layers may differ depending upon the coupling characteristics of the couplers in each emulsion layer.
  • my invention can be used in conjunction with many types of emulsion layers regardless of silver halide concentration to atfect contrast and grain favorably. While the faster and coarser grained emulsions of the concentration indicated are particularly adapted to use in our process, for some purposes the finer-grained emulsions can be used but the alteration in contrast and grain of the dye images contained therefrom is less pronounced.
  • the invention is particularly applicable to use in conjunction with multilayer color films containing colored color-forming coupler compounds such as disclosed in U. S. Patents 2,428,054 and 2,499,966.
  • mixed grain photographic elements such as described in U. S. Patents 2,490,749 and 2,490,751 are adapted to use in my process for the mentioned purposes of utilizing couplercontaining mixed-grain emulsions having silver halide concentrations of the order indicated and developing such emulsions with color developer compositions containing competing coupler compounds such as illustrated.
  • the soluble competing couplers forming diffusible dyes can be used in color developing compositions also containing soluble coupler compounds forming substantially nondifiusible dyes.
  • the nondifiusible dyes then remain in the photographic layer forming the color photographic image whereas the diffusible dye images formed along with them in color development leach out of the photographic layers in washing.
  • Such developer compositions are particularly useful for the development of dye images in emulsion layers devoid of coupler compounds; however, the etlect obtained may be somewhat difierent from the case when the competing coupler is in the developer and the image-forming coupler is in the emulsion.
  • a useful application of the process of my invention is in the production of monochrome fine-grain dye images in processes normally employing only black-and-white materials and processing.
  • processes in which a'fine-grain silver image is usually employed it was found that my process could be used to obtain the requisite fine-grain image with a substantial increase in the efiective emulsion speed, or alternately a reduction in graininess without loss of effective emulsion speed.
  • the process was carried out substantially as set forthin the above examples employing the image-forming coupler or mixture of different image-forming couplers in the emulsion and the competing coupler in the color-developing solution, the silver image being removed from the emulsion'following development leaving a fine-grained dye image.
  • both the image-forming coupler and the competing coupler can be used in the developer which permits the use of conventional black-and-white' sensitive materials.
  • a process for preparing colored photographic images which comprises developing an exposed silver halide emulsion layer with a color developing solution containing a primary aromatic amino silver halide developing agent, said development being carried out in the presence of both an image-forming coupler compound, and a competing coupler compound having the general formula:
  • R represents a member of the class consisting of 2.
  • R represents a member of the class consisting of hydroxyl, alkoxyl and amido groups
  • R1 and R2 each represent a member of the class consisting of a hydrogen atom and an acyl group
  • X and Y represent the carbon atoms necessary to complete a 6-membered ring
  • a process for preparing colored photographic images which comprises exposing to a subject a light-sensitive silver halide emulsion layer containing an image-forming coupler compound, developing the exposed emulsion layer with a color developing solution containing a primary aromatic amino silver halide developing agent, said development being carried out in the presence of 2,6-dihydroxyisonicotinic acid, to obtain in the exposed region of the developed emulsion layer both a difiusible dye from 2,6-dihydroxyisonicotinic acid and a nondifiusible dye image, from the image-forming coupler compound, and washing the difiusibledye from the emulsion layer.
  • a process for preparing colored photographic images which comprises exposing to a subject a light-sensitive silver halide emulsion layer containing an image-forming coupler compound, developing the exposed emulsion layer with a color' developing solution containing a primary aromatic amino silver halide developing agent, said development being carried out in the presence of 3,5-dihydroxybenzoic acid, to obtain in the exposed region.
  • the developed emulsion layer both a diffusible dye from 3,5-dihydroxybenzoic acid and a nonditfusible dye image from the image-forming coupler compound, and washing the diffusible dye from the emulsion layer.
  • R represents a member of the class consisting of hydroxyl, alkoxyl and amido groups
  • R1 and R2 each represent a member of the class consisting of a hydrogen atom and an acyl group
  • X and Y represent the carbon atoms necessary to complete a 6-membered ring
  • a light-sensitive photographic emulsion comprising silver halide, an image-forming coupler compound and a competing coupler compound having the general formula:
  • R represents amember of'th'e class consisting of hydroxyl, alkoxyl and amido groups
  • R1 and R2 each represent a member-of the class consisting of a hydrogen atom and an acyl group
  • X and Y represent the carbon atoms necessary to complete a 6-membered ring
  • a light-sensitive photographic emulsion comprising silver halide, an image-forming coupler compound and 2,6-dihydroxyisonicotinic acid.
  • a light-sensitivephotographic emulsion comprising silver-halide, an image-forming coupler compound and 3,5-dihydroxybenzoic acid.
  • a photographic color developing solution comprising an alkaline material, a primary aromatic amino silver halide developing agent, and 2,6-dihydroxyisonicotinic-acid.
  • a photographic color developing solution comprising an alkalinematerial, a primary aromatic amino silver halide developing agent, and 3,5-clihydroxybcnzoic acid.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US488957A 1955-02-17 1955-02-17 Controlling grain and contrast in color photography Expired - Lifetime US2742832A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE545183D BE545183A (US06653308-20031125-C00173.png) 1955-02-17
US488957A US2742832A (en) 1955-02-17 1955-02-17 Controlling grain and contrast in color photography
GB384/56A GB784479A (en) 1955-02-17 1956-01-05 Process of colour development in photography and light-sensitive emulsions and colour-forming developers therefor
FR1149695D FR1149695A (fr) 1955-02-17 1956-02-15 Procédé pour l'obtention d'images photographiques en couleurs
DEE11960A DE1002198B (de) 1955-02-17 1956-02-16 Verfahren zur Herstellung von farbenphotographischen Bildern

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US488957A US2742832A (en) 1955-02-17 1955-02-17 Controlling grain and contrast in color photography

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US2742832A true US2742832A (en) 1956-04-24

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US (1) US2742832A (US06653308-20031125-C00173.png)
BE (1) BE545183A (US06653308-20031125-C00173.png)
DE (1) DE1002198B (US06653308-20031125-C00173.png)
FR (1) FR1149695A (US06653308-20031125-C00173.png)
GB (1) GB784479A (US06653308-20031125-C00173.png)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998314A (en) * 1956-09-18 1961-08-29 Agfa Ag Color photography
US3132946A (en) * 1960-01-11 1964-05-12 Eastman Kodak Co Contact screens for photogravure
US3227554A (en) * 1959-04-06 1966-01-04 Eastman Kodak Co Photographic elements and processes utilizing mercaptan-forming couplers
US3402046A (en) * 1963-09-23 1968-09-17 Eastman Kodak Co Multilayer color photographic elements
JPS5096216A (US06653308-20031125-C00173.png) * 1973-12-24 1975-07-31
US4002477A (en) * 1973-11-28 1977-01-11 Eastman Kodak Company Diffusion transfer processes and elements using or containing inert transitional metal complex oxidizing agents
JPS5250230A (en) * 1975-10-20 1977-04-22 Fuji Photo Film Co Ltd Method for forming color photographic image

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE758971A (US06653308-20031125-C00173.png) * 1969-11-22 1971-05-17 Agfa Gevaert Nv

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998314A (en) * 1956-09-18 1961-08-29 Agfa Ag Color photography
US3227554A (en) * 1959-04-06 1966-01-04 Eastman Kodak Co Photographic elements and processes utilizing mercaptan-forming couplers
US3132946A (en) * 1960-01-11 1964-05-12 Eastman Kodak Co Contact screens for photogravure
US3402046A (en) * 1963-09-23 1968-09-17 Eastman Kodak Co Multilayer color photographic elements
US4002477A (en) * 1973-11-28 1977-01-11 Eastman Kodak Company Diffusion transfer processes and elements using or containing inert transitional metal complex oxidizing agents
JPS5096216A (US06653308-20031125-C00173.png) * 1973-12-24 1975-07-31
JPS53293B2 (US06653308-20031125-C00173.png) * 1973-12-24 1978-01-07
JPS5250230A (en) * 1975-10-20 1977-04-22 Fuji Photo Film Co Ltd Method for forming color photographic image

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GB784479A (en) 1957-10-09
DE1002198B (de) 1957-02-07
FR1149695A (fr) 1957-12-30
BE545183A (US06653308-20031125-C00173.png)

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