Classifications

• • 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
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers
  • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof

Definitions

• ABSTRACT Color reversal processes comprising a negative silver development step, followed by reversal color development with an aqueous alkaline color developing composition containing a 3-alkyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamine or a 3-alkoxy-N-alkyl-N-alkoxyalkyl-p-phenylenediamine color developing agent advantageously produce color image reproductions that are superior to those produced by prior art processes by enhancing interlayer and intralayer interimage effects produced in the negative development step, thus giving more complete correction for unwanted absorptions of the dyes, as well as (1) reducing color contamination of dye images caused by color fog, (2) increasing the dye yield per unitof silver, (3) forming dyes of superior light stability, and (4) providing processes that are less sensitive to pH changes.
• Color development of the differently sensitized emulsion layers in color photographic elements containing nondiffusible couplers is advantageously performed in a single color development step to produce a color negative image reproduction when this development step is the first development step, or to produce a color reversal image if a negative black-and-white development step followed by a step in which the residual unexposed and undeveloped silver halide is made developable and then color developed.
• diffusible couplers are used in the aqueous alkaline color developer solutions that are used to selectively color develop one silver halide emulsion layer at a time.
• the imagewise pattern of iodide ions released by development of the mixed silver halide crystals containing the higher mole percent iodide diffuses to the emulsion layer or emulsion layers that contain mixed silver halide crystals containing a lower mole percent iodide and produces an image-wise inhibition of the latent image development resulting in an increase in residual silver halide in the lower iodide-containing layer according to image development in the higher iodide containing layer.
• the increase in residual silver halide that remained in the lower iodide-containing layer after negative (i.e., black-and-white) development results in corresponding increases in dye formation.
• Color development processes are desired which will enhance interimage effects and give improved color reproduction.
• Color development processes use active aromatic primary amine color developing agents; however, not all silver halide grains containing latent image centers are developed to silver and dye. These so-called dead grains are wasted in color photographic development. Color development processes are desired that make more efficient use of latent image-exposed silver halide grains so that the ratio of dye produced to exposed silver halide is larger than the ratio produced in processes known before our invention.
• Color development processes are desired that produce less fog or color development in non-image areas while they produce good dye density levels in image areas.
• Color development processes are desired that are less sensitive to pH than known processes.
• Color development processes are also desired which produce dye images having better stability to prolonged exposure to heat, high humidities and/or light.
• Another object of our invention is to provide anovel color development process that produces improved color reproduction in subtractive color processes as a result of enhanced interimage effects, as well as lower fog in unexposed areas, higher dye densities in exposed areas, and a color development process that is less sensitive to pH.
• Another object of our invention is to produce a novel color development process that produces improved color reproduction by developing substantially all silver halide grains that contain latent images and leaving substantially no dead silver halide grains.
• Such interlayer and intralayer interimage effects are substantially enhanced in accordance with the invention by color developing residual undeveloped silver halide in the presence of photographic couplers to form nondiffusible dyes substantially complementary in color to the light sensitivity of the respective silver halide emulsion layers in an aqueous alkaline color developing composition containing a 3-alkyl-N-alkyl-N-alkoxyalkyl-pphenylenediamine color developing agent or a 3-alkoxy-N- developing agent in which the several alkyl and alkoxy groups are lower alkyl and lower alkoxy groups.
• These color developing agents used according to our invention include those having the formula:
• n is an integer of 2 to 4;
• R is an alkyl group having one to four carbon atoms, e.g., methyl, ethyl, propyl, butyl, etc.; and
• R' is an alkyl group having from one to four carbon atoms,
• the photographic couplers present during the color development step are either incorporated in the appropriately sensitized silver halide emulsion layer as nondiffusible couplers, in which case the color development of all three emulsion layers is advantageously accomplished with a single development step with one color developing solution containing a 3-a1kyl-N-alkyl-N-alkoxyalkyl-p-phenylenediamine or a 3-alkoxy-N-alkyl-N-a1koxyalkyl p-phenylenediamine color developing agent; or, diffusible couplers are used in developer solutions, for example, a diffusible cyan-dye-forming coupler is used in a cyan developing composition to color develop the red-sensitive layer, a diffusible yellow-dye-forming coupler is used in a yellow developing composition to color develop the blue-sensitive layer and a diffusible magenta-dye-forming coupler is used in a magenta developing composition to color develop the green-sensitive layer (
• Black-and-white development is advantageously done with an aqueous alkaline composition
• an aqueous alkaline composition comprising any non-dyeforming silver halide developing agent, preferably at least one of hydroquinone, p-methylaminophenol, 1-phenyl-3- pyrazolidonc, 4,4-dimethyl-3-pyrazolidone, etc.
• the undeveloped silver halide is made developable by any appropriate means, such as, exposure to light, treatment with a chemical fogging agent, e.g., an alkali metal borohydride, an amine borane, etc., prior to or during the color development step.
• a chemical fogging agent e.g., an alkali metal borohydride, an amine borane, etc.
• the emulsion layers after black-and-white development are sequentially treated in a selective way to make residual silver halide in one emulsion layer at a time developable and then color developed before silver halide in another emulsion layer is made developable, etc.
• a red-sensitive emulsion, a green-sensitive emulsion, a bleachable yellow colored filter layer and a bluesensitive emulsion layer it is advantageous to selectively reexpose the bottom red-sensitive layer with red light through the support, cyan develop, wash, selectively re-expose the blue-sensitive layer directly with blue light, yellow develop, wash, re-expose the middle green-sensitive layer with white light or make this layer developable with a chemical fogging agentjust prior to or during magenta development.
• the film is washed and the silver and any residual silver halide is removed by treatment with a silver bleach followed by a fixing bath to leave the unobstructed multicolor dye image reproduction in the photographic element.
• Conventional alkali metal ferricyanide bleach baths and alkali metal thiosulfate fix baths are used advantageously to bleach and then fix the color developed elements.
• Typical representative examples of the color developing agents of Formula I are the following:
• hydrochloric acid salts the sulfuric acid salts, the phosphoric acid salts, the oxalic acid salts, p-toluenesulfonic acid salts, the benzene disulfonic acid salts and the naphthalene disulfonic salts are used to advantage in our process.
• the color developing agents of Formula I are used advantageously in aqueous alkaline color developer solutions over a wide range of concentrations, with an operable range of from about 0.5 g/] to about 15 g/l and a preferred range of from about 1.0 g/l to about 12.0 g/l.
• addenda used to advantage in these developer compositions include alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfites, alkali metal sulfates, alkali metal carbonates, alkali metal hydroxides, alkali metal metaborates, a1- kali metal phosphates, ethylenediamine, citrazinic acid, antifogging agents, e.g., S-nitrobenzimidazole, etc., an auxiliary developing agent, e.g., l phenyl-3-pyrazolidones, a stabilizer for developing agents (e.g., diethyl hydroxylamine, dihydroxyacetone, glycolaldehyde, glyceraldehyde, dihydroxymaleic acid, etc., sodium hexametaphosphate, etc.), etc.
• a typical color developing composition used in our process for a photographic element that contains incorporated couplers is as follows:
• Color Developing Composition 1 Benzyl alcohol 0-12 ml. Alkali metal hexametaphosphate O-3 g. Alkali metal sulfite 2-20 g. Tri alkali metal phosphate -l2H O l0-60 g.
• Alkali metal iodide (0.1% soln.) O-15 ml.
• Color developing agent of Formula 1 05-15 g. Ethylenediamine sulfate 0-20 g. Citrazinic acid 0-5 Dithiooctanediol 0-5 g.
• alkali metal hydroxide sodium, potassium, lithium, etc.
• Typical color developing compositions used to advantage in processes of our invention for photographic elements that do not contain couplers are as follows:
• Cyan and Yellow Color Developing Compositions In this composition, a phenol or naphthol cyan-die-forming coupler is used in cyan developing compositions and an open chain acyl acetamide type yellow-dye-forming coupler is used in yellow developing compositions.
• Antifoggants such as, 5- nitrobenzimidazole, 5-nitrobenzimidazole-6-nitrate, etc., are used to advantage as the antifoggant.
• Any ofthe alkalis used in photogra hic developer solutions are used to advantage in the color developing composition including alkali metal hydroxides, alkali metal carbonates, borax, etc.
• the alkali metals used to advantage to make the compounds of the cyan and yellow color developing compositions and the following magenta color developing composition are sodium, potassium and lithium.
• MAGENTA COLOR DEVELOPING COMPOSITIONS These are the same as the cyan and yellow developing compositions, except that they do not contain an auxiliary developing agent or any antifogging agent, but they do contain in addition to the cOmponents listed above:
• Alkali metal thiocyanate 0.3-5 g./l.
• a chemical fogging agent for silver halide 0-2 g./l.
• Chemical fogging agents used to advantage include the nucleating agents of Hanson et al., U.S. Pat. No. 3,246,987, e.g., the amine boranes (e.g., trimethylamine borane, diethylamine borane, triethylamine borane, tert-butylamine borane, pyridine borane, 2,6-lutidine borane, etc.), the polyamine boranes (.e.g, ethylenediamine diborane, hydrazine diborane, etc.), a phosphine borane (e.g., dimethylphosphine borane), an arsine borane (e.g., dimethylarsine borane), a stilbene borane (e.g., dimethylstilbene borane a borazine (e.g., borazine, N,N',N-trimethyl borazine, N,N,N"-trime
• a typical chemical fogging bath has the composition:
• any of the well-known diffusible couplers used in the color developer solutions are used to color develop our photographic elements that do not contain incorporated couplers.
• These couplers include those described by U.S. Pat. Nos. 2,266,452, 2,295,009, 2,313,586, 2,362,598, 2,369,929, 2,772,162, 3,002,836, 2,311,082, 2,353,205, 2,369,489, 2,600,788, 2,343,703, 2,899,306, 2,115,394, 2,108,602, 2,113,330, 2,271,238, 2,289,805, 2,439,352, etc.
• the multicolor, multilayer color photographic elements processed to advantage according to our invention are advantageously coated a a wide variety of transparent film supports including cellulose nitrate film, cellulose ester film, po1y(viny acetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials as well as glass.
• the redgreenand bluesensitive silver halide emulsion layers are arranged in various orders on the film supports.
• a red-sensitized silver halide emulsion layer is advantageously coated over the support, followed in succession by a green-sensitized silver halide emulsion layer and a blue-sensitive silver halide emulsion layer.
• one type of color photographic elements processed according to our invention contains a nondiffusible cyan-dye-forming coupler in the red-sensitized layer, a nondiffusible magenta-dye-forming coupler in the green-sensitized layer and a nondiffusible yellow-dye-forming coupler in the blue-sensitive layer, while another type does not contain nondiffusible couplers incorporated in the emulsion layers.
• Non-sensitive hydrophilic colloid interlayers are advantageously used between one or more of the light-sensitive layers. It is advantageous to have a bleachable yellow-colored filter between the blue-sensitive and green-sensitive layers.
• hydrophilic colloids used in photographic elements are advantageously used in the light-sensitive and non light-sensitive hydrophilic colloid layers of elements processed by our process.
• Hydrophilic colloids used alone or in combination include both naturally-occurring substances, (such as, proteins, e.g., gelatin, gelatin derivatives, etc., cellulose derivatives, polysaccharides, such as, dextrose, gum arabic and the like) and synthetic polymeric substances, such as, water-soluble polyvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.
• any of the ordinarily employed silver halide developing-out emulsions e.g., silver chloride, silver chlorobromide, silver chlorobromoiodide, silver bromide, silver bromoiodide developing-out emulsions are used to advantage in elements processed according to our invention.
• Particularly useful results are obtained with mixed silver halide emulsions comprising an iodide, e.g., silver bromoiodide, silver chlorobromoiodide, silver chloroiodide, etc., containing mixed silver halide crystals wherein the iodide comprises about 1 to about 20 mole percent of the halide of the mixed silver halide crystals.
• any silver halide emulsion can be used provided the emulsion in at least one layer differs from the emulsion in at least one other layer as to development rate and/or excess of halide in the silver halide.
• certain addenda are advantageously used in one or more of the silver halide emulsion layers to cause interlayer and intralayer interimage effects driving the black-and-white development.
• diffusible 3-hydrogen substituted 4-thiazoline-2-thiones includedwherein X represents alkyl, e.g., methyl or ethyl, an alkyl substituent containing at least one hydroxyl group, e.g., hydroxymethyl, B-hydroxyethyl, gluco or arabino, or an alkyl substituent having at least one carbamyl-containing group, e.g., formyl, carboxyl, ethoxy carbonyl or acetoxy methyl; and Z is is independently selected from a value given for X and preferably represents hydrogen.
• X represents alkyl, e.g., methyl or ethyl, an alkyl substituent containing at least one hydroxyl group, e.g., hydroxymethyl, B-hydroxyethyl, gluco or arabino, or an alkyl substituent having at least one carbamyl-containing group, e.g., formyl, carboxyl, e
• the 4- thiazoline-Z-thione compound is one which can enolize to its correspondingmercaptan form at any suitable time, such as, when the 4-thiazoline-2-thione is added to a hydrophilic colloid layer containing light-sensitive silver halide.
• Representative compounds include 4-thiazoline-4-carboxaldehyde-2- thione, 5-carbethoxy-4-methyl-4-thiazoline-2-thione, 4-carboxy-4-thiazoline-2thione, 4-carboxy-5-methyl-4-thiazoline- 2-thione, 4-(D-arabino-tetraacetoxybutyl)-4-thiazoline-2- thione, 4-(D-arabino-l ,2,3,4-tetrahydroxybutyl)-4-thiazoline- 2-thione, 4-hydroxymethyl-4-thiazoline-Z-thione, 4-methyl-4- thiazoline-2-thione.
• the 3-hydrogen substituted 4-thiazoline-2-thiones are advantageously incorporated in silver halide emulsion layers in the range of from about 5.0 mg to about 500 mg of the addenda per mole of silver and especially in the range of from 100 mg to 200 mg.
• a useful concentration range is from about 0.1 mg to about 1.0 g per liter of solution and, preferably, in the range from about 1.0 mg to 500mg per liter.
• the silver halide emulsions used in elements processed according to our invention are advantageously spectrally sensitized with any of the appropriate cyanines, merocyanines, complex cyanines, complex merocyanines, styryls, hemicyanines, etc.
• These dyes contain the usual basic nuclei, e.g., thiazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, naphthoselenazole, quinoline, etc., or in the case of merocyanine dyes, an acidic nucleus, e.g., hydantoin, 2-thiohydantoin, oxazolidone, pyrazolone, etc.
• Such dyes are described in the Brooker et al. U.S. Pat. Nos. 2,185,182, 2,241,237; Carroll U.S. Pat. Nos.
• Photographic silver halide emulsions can also contain such addenda as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc.) (see Baldsiefen, U.S. Pat. No. 2,540,685; Damschroder, U.S. Pat. No. 2,597,856 and Yutzy and Leermakers, U.S. Pat. No.
• chemical sensitizers e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.)
• gold compounds e.g., potassium chloroaurate, auric trichloride, etc.
• 2,597,915 various palladium compounds, such as, palladium chloride (Baldsiefen et al., U.S. Pat. No. 2,540,096), potassium chloropalladate (Stauffer et al. U.S. Pat. No. 2,598,079), etc., or mixtures of such sensitizers; antifoggants, such as, ammonium chloroplatinate (Trivelli and Smith, U.S. Pat. No. 2,566,245), ammonium chloroplatinite (Trivelli and Smith, U.S. Pat. No. 2,566,263), benzotriazole, nitrobenzimidazole, S-nitroindazole, benzidine, mercaptans, etc.
• hardeners such as, formaldehyde or chrome alum (Miller U.S. Pat. No. 1,763,533), glyoxal (Brunken, U.S. Pat. No. 1,870,354), dibromacrolein (Bloch et a1, British Pat. No. 406,750), aziridine hardeners of Burness, U.S. Pat. No. 2,964,404; Allen ct al., U.S. Pat. No. 2,950,197; Yudelson, U.S. Pat. No.
• any of the color-forming couplers used in photographic elements are used to advantage in photographic materials for our process.
• lncluded among the phenol and naphthol cyan dyel orming couplers used to advantage are those described by the following U.S. Pat. Nos. 2,423,730, 2,474,293, 2,521,908, 2,725,291, 2,801,171, 3,253,294, etc.
• lncluded among the ketomethylene yellow-dye-forming couplers used to advantage are those described in U.S. Pat. Nos. 2,298,443, 2,778,658, 2,801,171, 2,875,057, 3,253,924, 3,277,155, etc.
• lncluded among the 5-pyrazolone magenta dye-forming couplers used to advantage are those described in U.S. Pat. Nos. 2,600,788, 2,801,171, 3,252,924, etc.
• Dispersing agents for color-forming couplers and the dispersing techniques used to advantage include those set forth in Jelley et al., U.S. Pat. No. 2,322,027; Mannes et al., U.S. Pat. No. 2,304,940; Fierke et al., U.S. Pat. No. 2,801,l7l,etc.
• the color developing agents of Formula I are prepared by reacting the appropriate w-alkoxyalkyl chloride or bromide with the appropriate N-ethyl-3-alkylaniline or N- ethyl-3-alkoxyaniline.
• the tertiary anilines formed by this reaction are then either nitrosated or azo-coupled, followed by catalytic hydrogenation to give the corresponding p-phenylenediamines.
• Some of the developing agents of Formula 1 are advantageously isolated as the acid salts.
• the di-p-toluenesulfonic acid salt of Color Developing Agent 3 is advantageously prepared by the following sequence of reactions:
• N-(B-Ethoxyethyl)-N-ethyl-3-methylani1ine A mixture of g (1 mole) of N-ethyl-3-methylaniline, 153 g (1 mole) of 2-bromoethyl ethyl ether (purified by treatment with sodium bicarbonate and distillation), 88.2 g (1.05 mole) of sodium bicarbonate, 1,100 ml of ethanol and 290 ml of water are refluxed for a total of 64 hours.
• the ethanol is removed by distillation and the oil layer is extracted with ether; the ether extracts are dried and concentrated, followed by distillation of the residual oil under reduced pressure. After removal of the lower boiling foreruns, the fraction, b.p. 9295 C/lmm (overheats readily), is collected. The yield of l is approximately 70 percent.
• the mixture is cooled to about 25 C and allowed to stand undisturbed overnight.
• the developer salt is filtered off and washed in funnel with small portions of isopropyl alcohol.
• the yield of Developing Agent 3, mp. 2l4216 C, is approximately 70 percent.
• the di-p-toluenesulfonic acid salt of Color Developing Agent 5 is advantageously prepared similarly to developing agent (3), using N-ethyl-3-methoxyaniline and 2-bromoethyl methyl ether as starting materials.
• N-Ethyl-3-methoxy-N-(B-methoxyethyl)-aniline A mixture of 100 g (0.661 mole) of N-ethyl-3-methoxyaniline, 92 g (0.661 mole) of 2-bromoethyl methyl ether, 55.8 g (0.6665 mole) of sodium bicarbonate, 1,000 ml of ethanol and 280 ml of water is refluxed for a total of 68 hours. The alcohol is removed under partial vacuum and the oil layer extracted with ether; the ether extracts are dried and concentrated. The residual oil is then distilled under reduced pressure. The yield of ill, b.p. l49-l5 1 C/8mm, is 35 percent.
• the di-p-toluenesulfonic acid salt of 4-amino-N-ethyl-3- methoxy-N-(B-methoxyethyl)aniline Developing Agent 5' Exactly 486 g (0,127 mole) of the azo dye, IV, is reduced on Parr shaker, using 300 ml of absolute alcohol and Raney nickel as catalyst. When complete, the catalyst is filtered off, washed on funnel with more alcohol. A total of 4,84 g (0.0254 mole) of p-toluenesulfonic acid (hydrate) in 50 ml of ethanol is added; no precipitate occurs and the solution is concentrated to dryness under partial vacuum.
• the gummy residue is then dissolved in a small quantity of absolute alcohol and a large excess of ethyl ether is added; the developer salt again comes out as a gum; the solution is cooled thoroughly (refrigerator) to precipitate the suspension and then the etheralcohol layer is decanted. This treatment is repeated twice more to remove all of the regenerated 2,5-dichloroaniline. Finally, the developer salt is slurried thoroughly with ether only, gradually becoming crystalline; it is dried in a vacuum oven. The yield of Developing Agent 5, mp. l60l62 C, is 62 percent.
• the di-p-toluenesulfonic acid salt of Color Developing Agent 1 is made in a manner similar to the synthesis described for the corresponding acid salt of Color Developing Agent 5, excepting that an equimolar amount of N-ethyl-3- methylaniline is used in place of N-ethyl-3-methoxyaniline.
• the di-p-toluenesulfonic acid salt of Color Developing- Agent 2 is made in a manner similar to the synthesis described for the corresponding acid salt of Color Developing Agent 5, excepting that an equimolar amount of arbromobutyl methyl ether is used in place of 2-bromoethyl methyl ether.
• the di-p-toluenesulfonic acid salt of Color Developing Agent 4 is advantageously made in a manner similar to that described for the corresponding acid salt of Color Developing Agent 3, excepting that an equimolar amount of N-ethyl-3- propylaniline is used in place of N-ethyl-3-methylaniline.
• Still other color developing agents of Formula I are made using the syntheses illustrated herein using the appropriate intermediates.
• Example 1 Two samples of a multilayer color film having a cellulose acetate film support coated in succession with a red-sensitive gelatino silver bromoiodide emulsion layer, a green-sensitive gelatino silver bromoiodide emulsion layer, a gelatin layer containing bleachable yellow colored Carey Lea silver and a blue-sensitive gelatino silver bromoiodide emulsion layer are sensitometrically exposed to a step tablet and processed at 27 C through the following process sequence:
• rQ-P pouPo some 5 BWWW' Film Sample I is yellow developed in the yellow developing composition having 1.06 g/l of Color Developing Agent B, i.e., N-ethyl-N(B-hydroxyethyl)-3-methyl-p-phenylenediamine and Film Sample II is yellow developed in the yellow developing composition having 2.0 g/l of Color Developing Agent 1, i.e., N-ethyl-N-methoxyethyl-3-methyl-p-phenylenediamine.
• Polyoxyethylcne (in. wt. 4000) 1.0 g. Hexylene glycol 10.0 ml.
• a S-pyrazolone coupler of U.S. Pat. No. 3,152,896 1.67 g.
• Sodium hydroxide 0.32 g. Water to make 1 liter
• the bleach solution is a conventional alkali metal bromide and alkali metal ferricyanide bleach, and the hypo-fix a conventional alkali metal thiosulfate fixing bath.
• a comparison of processed Film Sample I given the prior art process with Film Sample 11 given our process shows that our process produces better color reproductions of the original step tablet than the prior art process with brighter blue images.
• Example 2 Example 1 is repeated, but comparing the prior art process used in Example 1 against each of five of our processes in which Color Developing Agents 2, 3, 4, 5 and 6, respectively, are substituted in equimolar amounts for Color Developing Agent 1 in the yellow developing composition. In each instance, our processes produce color reproductions that are superior to the reproduction produced by the prior art process with brighter blue images.
• Example 3 Two samples, I and II, of a multilayer, multicolor photographic element which element produces an interimage effect comprising a cellulose acetate film support coated in succession with a red-sensitive gelatino silver bromoiodide emulsion layer (with 6 mole percent iodide) containing a mixture of nondiffusible cyan dye-forming couplers, i.e., a naphthamide coupler of U.S. Pat. No. 2,474,293 and a phenol coupler of U.S. Pat. No.
• Example 4 Two samples, 111 and IV, of the multilayer, multicolor element described in Example 3 are each given an exposure that is used to check for interimage effects. The exposure comprises a stepped exposure to red light, superimposed by a stepped exposure to blue light and a flash to green light. Exposed Sample III is given the prior art process described in Example 3 for Sample I and exposed Sample IV is given our process described in Example 3 for Sample II. A comparison of the density vs.
• Example 5 A multilayer, multicolor photographic element like the element described in Example 3, except that a nondiffusible phenol cyan-dye-forming coupler of U.S. Pat. No. 2,423,730 is used in the red-sensitive layer and a nondiffusible aacylacetamide yellow-dye-forming coupler is used in the bluesensitive layer in place of the cyan couplers and the yellow coupler used in Example 3, is made. Samples I and II of this element are exposed as described in Example 4.
• Exposed Samples I and II are processed with the prior art process and with our process, each as described in Example 3.
• a comparison of the density vs. exposure curves plotted for the processed films shows that the unwanted green light absorption in the cyan and yellow dye images is corrected by enhancement with our process of the interimage effect while the unwanted light absorptions are undercorrected by a considerably amount with the prior art process.
• Example 6 Four samples, identified as V, VI, VII and VIII, of the multilayer, multicolor photographic element described in Example 3 are sensitometrically exposed to a step tablet and processed. Samples V and VI are processed in the prior art process described in Example 3 with the color developing solution pH adjusted at 10.4 for Sample V and adjusted at l 1.6 for Sample VI.
• Samples VII and VIII are processed in our process described in Example 3 with the color developer pH adjusted at 10.4 for Sample VII and at 1 1.6 for Sample VIII.
• the change in developed cyan dye density caused by increasing the pH of the color developer from 10.4 to 1 1.6 at an exposure level that gives a cyan density between 1 and 2 at a pH of 10.4, is determined for each process. This is repeated for the developed yellow dye and the developed magenta dye. The results are summarized in the following table.
• a color photographic process for treating an imagewise exposed multicolor photographic element comprising a transparent film support having coated thereon silver halide emulsion layers sensitive to at least two of the red, green and blue areas of the visible spectrum and black-and-white developing said silver halide emulsion layers to silver images in areas of exposure to produce interimage effects
• the improvement which comprises enhancing said interimage effects by color developing resulting undeveloped silver halide in the presence of photographic couplers to form nondiffusible dyes substantially complementary to the sensitivity of the respective silver halide emulsion layers in an aqueous alkaline color developing composition containing a color developing agent selected from the group consisting of a 3-alkly-N-alkyl-N-alkoxyalkyl-p-phenylenediamine and a 3-alkoxy-N-alkyl-N-alkoxyalkyl-p-phenylenediamine.
• black-and-white developing is carried out with an aqueous alkaline developing composition containing at least one developing agent selected from the class consisting of hydroquinone, pmethylaminophenol, l-phenyl-3-pyrazolidone and 4,4- dimethyl-l-phenyl-pyrazolidone.
• a color photographic process for treating an imagewise exposed multicolor, multilayer photographic element comprising a transparent film support having coated thereon red, green and blue-sensitive silver bromoiodide emulsion layers and black-and-white developing said silver bromoiodide emulsion layers to silver images in areas of exposure to produce interimage effects
• the improvement which comprises 1) making residual unexposed and undeveloped silver bromoiodide developable and (2) thereafter enhancing said interimage effects by color developing said undeveloped silver bromoiodide in the presence of photographic couplers to form nondiffusible dyes substantially complementary to the sensitivity of the respective silver bromoiodide emulsion layers in an aqueous alkaline color developing composition containing a color developing agent having the formula:
• n is an integer of 2 to 4; R is an alkyl group having one to four carbon atoms, and R is an alkyl group having one to four carbon atoms or an alkoxy group having one to four carbon atoms.
• said light-sensitive layers of said black-and-white developed photographic element are 2. treating said element with an aqueous alkaline cyan color developing composition containing a diffusible cyan-dyeforming coupler and an aromatic primary amine color developing agent which develops said developable silver halide in said red-sensitive layer to a silver image and a corresponding image-wise pattern of oxidized color developing agent which reacts with said cyan-dye-forming coupler to form a corresponding nondiffusible cyan dye image,
• n is an integer of2 to 4;
• R is an alkyl group having one to four carbon atoms, and R is an alkyl group having one to four carbon atoms or an alkoxy group having one to four carbon atoms.
• said yellow color developing composition contains a diffusible acylacetanilide yellow-dye-forming coupler and a color developing agent selected from those having the formula:
• acetanilide yellow-dye-forming coupler and a color developing agent selected from those having the formula:
• said yellow color developing composition contains a diffusible acylacetanilide yellow-dye-forming coupler and a color developing agent selected from the class consisting of N-ethyl-N-methoxyethyl- 3-methyl-p-phenylenediamine, N-ethyl-N-methoxybutyl-3- methyl-p-phenylenediamine, N-ethyl-N-ethoxyethyl-3- methyl-p-phenylenediamine, N-ethyl-N-methoxyethyl-3- propyl-p-phenylenediamine, N-ethyl-N-methoxyethyl-3- methoxy-p-phenylenediamine and N-ethyl-N-butoxyethyl-3- methyl-p-phenylenediamine.
• a diffusible acylacetanilide yellow-dye-forming coupler and a color developing agent selected from the class consisting
• said yellow color developing composition contains a diffusible acylacetanilide yellow-dye-forming coupler and N-ethyl-N-methoxyethyl-3- methyl-p-phenylenediamine.
• said yellow color developing composition contains a diifusible acylacetanilide yellow-dye-forming coupler and N-ethyl-N-methoxyethyl-3- methoxy-p-phenylenediamine.
• nondiffusible cyan, magenta and yellow-forming photographic couplers are incorporated in the red, green and blue-sensitive silver bromoiodide emulsion layers, respectively, and said cyan coupler is selected from the class consisting of a phenol and a naphthol; said magenta coupler is a S-pyrazolone coupler and said yellow coupler is an acylacetacetamide.
• said silver bromoiodide emulsion layers contain in the range of from about 1 to 20 mole percent iodide and at least one of said silver bromoiodide emulsion layers contains at least one mole percent more iodide than at least one of the other silver bromoiodide emulsion layers.

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• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (19)

Citations (8)

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• 1970
  • 1970-12-03 US US94992A patent/US3658525A/en not_active Expired - Lifetime
• 1971
  • 1971-11-04 CA CA126,842A patent/CA955102A/en not_active Expired
  • 1971-12-03 FR FR7143406A patent/FR2117338A5/fr not_active Expired
  • 1971-12-03 BE BE776262A patent/BE776262A/xx not_active IP Right Cessation
  • 1971-12-03 JP JP46097243A patent/JPS5121582B1/ja active Pending
  • 1971-12-03 CH CH1769871A patent/CH536502A/fr not_active IP Right Cessation

Patent Citations (8)

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