US3311476A - Two-equivalent couplers for color photography - Google Patents

Two-equivalent couplers for color photography Download PDF

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US3311476A
US3311476A US247302A US24730262A US3311476A US 3311476 A US3311476 A US 3311476A US 247302 A US247302 A US 247302A US 24730262 A US24730262 A US 24730262A US 3311476 A US3311476 A US 3311476A
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group
couplers
coupler
forming
light
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Loria Anthony
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to GB50607/63A priority patent/GB1077873A/en
Priority to GB4871/67A priority patent/GB1077875A/en
Priority to FR958168A priority patent/FR1385697A/fr
Priority to BE641871A priority patent/BE641871A/xx
Priority to US584936A priority patent/US3432521A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C07D231/48—Oxygen atom in position 3 or 5 and nitrogen atom in position 4 with hydrocarbon radicals attached to said nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/28—Two oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • 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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • 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
    • G03C7/34—Couplers containing phenols
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors

Definitions

  • This invention relates to photography and particularly to compounds which form dyes upon coupling with oxidized color developing agent and to photographic elements containing these compounds.
  • the color forming coupler may be either in the developer solution or incorporated in the light-sensitive photographic emulsion layer so that during development it is available in the emulsion layer to react with the color developing agent that is oxidized by silver image development.
  • Diifusible type couplers are used in color developer solutions.
  • Fischertype couplers and hydrophobic couplers are incorporated in photographic emulsion layers.
  • couplers are selected which form nonditfusing dyes.
  • the dye image used for image transfer processes should be diffusible but capable of being mordanted or fixed in the receiving sheet. For this purpose a coupler is selected which will produce this type of dye.
  • Conventional color-forming couplers are four-equivalent, that is, they require the development of four molecules of exposed silver halide in order to supply one molecule of oxidized color developing agent that is free to couple and form one molecule of dye.
  • Two-equivalent couplers require the development of only two molecules of exposed silver halide to bring about the formation of one molecule of dye.
  • Two-equivalent couplers are very desirable for color photography, since only one-half the usual amount of silver halide is needed and the lightsensitive coatings can thus be made thinner. Certain of the available two-equivalent couplers tend to produce more stain than is desired, and others have not had the desired coupling reactivity. New classes of two-equivalent couplers are needed.
  • Another object of my invention is to provide valuable acyloxy substituted two-equivalent couplers for forming cyan dye images and magenta dye images that have good spectral absorption characteristics, and good stability to prolonged exposure to light, heat and high humidity.
  • Another object is to provide acyloxy substituted twoequivalent couplers which have good coupling reactivity and which include the difiusible type coupler, the Fischer type and the hydrophobic type couplers which are readily incorporated in light-sensitive hydrophilic colloidsilver halide emulsion layers in a wide range of coupler to solvent ratios.
  • R represents a group selected from the class consisting of an alkyl group having from 1 to 22 carbon atoms, e.g., methyl, 3-pentadecylphenoxymet-hyl, ethyl, phenylethyl, n-propyl, isopropyl, a-(ZA-di-tert-amylphenoxy)propyl, o-su lfobutyl, sec-butyl, tert-butyl, docosyl, chloromethyl, trifiuoromethyl, Z-hydroxymethl, B-carboxethy l, 2-(2,4,6-trichlorophenyl)ethyl, 2-aminoethyl,
  • a terpenyl group e.g., 7,7-dimethylnorborny-l, 2-alkyl-7,7-dimethylnorbornyl radicals in which the alkyl group has from 1 to 18 carbon atoms, such as methyl, butyl, octadecy l, etc., for example, 2-methyl-7,7-dimethylnorbornyl, 2-octadecyl-7,7-dimethylnorbornyl, etc., a 2-ary
  • R represents the hydrogen atom, a primary, secondary or tertiary alkyl group having from 1 to 22 carbon atoms as defined for R an aryl group as defined for R a heterocyclic group as defined for R attached
  • My two-equivalent couplers are characterized by having an acyloxy group on the coupling position of the coupler which gives them good coupling reactivity and other valuable properties.
  • Some of my nondiffusible couplers have good coupling reactivity when incorporated in emulsion layers with no high-boiling coupler solvents, while the others are dispersed to advantage in high-boiling solvents solutions in a wide range of coupler to solvent ratios.
  • magenta-forming and cyan-forming couplers will illustrate but not limit my invention.
  • any of the well known primary aromatic amino color-forming silver halide developing agents such as the phenylenediamines, e.g., diethyl-p-phenylenediamine hydrochloride, monomethyl-pphenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, Z-amino-5-diethylaminotoluene hydrochloride, 2-amino-5(N-ethyl-N-lauryl)toluene, N- ethyl-[i-methanesulfonamidoethyl 3 methyl-4-aminoaniline sulfate, N-ethyl B methanesulfonamidoethyl- 4-aminoaniline, 4-N-ethyl
  • Vari ous other materials may be included in the developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisnlfite, bromide, iodide, etc., and the thickening agents used in viscous developer compositions such as are described in copending Whitmore and Mader U.S. Ser. No. 222,105, filed Sept. 7, 1962, now U.S. Patent 3,227,550.
  • the following is a typical developer solution given to illustrate but not limit the invention.
  • the ditfusible couplers of my invention are used to advantage in emulsion layers when incorporated by the methods described by Mannes et al. U.S. Patent 2,304,940, issued Dec. 15, 1940.
  • Cyan coupler No. 6 illustrates a type of coupler that is used to advantage in color developer solutions (with imageforming couplers) as competing couplers, since the dyes formed are ditfusible and are washed out of the emulsion layer during processing.
  • other couplers of my invention can be used as competing couplers providing a solubilizing group or groups are present on the R R R R R R or R groups.
  • the other coupler examples used to illustrate my invention are nondiifusing and are used to advantage in photographic emulsion layers.
  • Cyan couplers N0. 8 and No. 10 illustrate those that are incorporated as Fischer type couplers.
  • the other nondiffusing couplers are incorporated in emulsion layers by methods such as are described by Mannes et al. U.S. Patent 2,304,939, issued Dec. 15, 1942, Jelley et al. U.S. Patent 2,322,027, issued June 15, 1943, etc., in which high-boiling organic solvents are used to dissolve the coupler, and by methods described in Vittum et al. U.S. Patent 2,801,170, and Fierke et a1.
  • emulsion layers containing rny couplers be made thinner because they require only one-half the silver halide required by conventional couplers (i.e., four-equivalent couplers) but some of my couplers are sufficiently reactive that they do not require any high-boiling coupler solvent that is usually required by couplers.
  • Thin image-forming layers are very desirable because they-cause less light scattering and produce sharper images.
  • My-nondifiusing cyan coupler No. 8 forms diflusible dye images upon color development and is used to advantage either in image transfer elements or in emulsion layers that contain my coupler as a nonirnage-forming competing coupler along with an image-forming coupler.
  • nonditfusing couplers used to illustrate my invention form nondiffusing dyes and are used to advantage in any photographic element where incorporated image-forming couplers are desired.
  • My couplers are used in the color development of photographic hydrophilic colloid-silver halide emulsion layers of the developing-out type either in the color developer solution or in the emulsion layer.
  • the emulsions may contain silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chloro bromoiodide, etc., as the light-sensitive material.
  • Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
  • Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in U.S. Patent 2,286,215, of Lowe; a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 1926% as described in U.S. Patent 2,327,808 of Lowe and Clark, a water-soluble ethanolamine cellulose acetate as described in U.S.
  • Patent 2,322,085 of Yutzy a polyacrylamide having a combined acrylamide content of 30-60% and a specific viscosity of 0.251.5 on an imidized polyacrylamide of like acrylamide content and viscosity as described in U.S. Patent 2,541,474 of Lowe, Minsk and Kenyon; zein as described in U.S. Patent 2,563,791 of Lowe; a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in U.S. Patent 2,768,154 of Unruh and Smith, or containing cyano-acetyl groups, such as the vinyl alcohol-vinyl cyano-acetate copolymer as described in U.S.
  • Patent 2,808,331 of Unruh, Smith and Priest; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in U.S. Patent 2,852,382 of Illingsworth, Dann and Gates.
  • the emulsions used in the photographic element of my invention can be chemically sensitized by any of the accepted procedures.
  • the emulsions can be digested with naturally active gelatin, or sulfur compounds can be added, such as those described in Sheppard U.S. Patent 1,574,944; Sheppard and Punnett U.S. Patent 1,623,499; and Sheppard and Brigham U.S. Patent 2,410,689.
  • the emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum.
  • the noble metals such as ruthenium, rhodium, palladium, iridium and platinum.
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060 and as antifoggants in higher amounts, as described in Trivelli and Smith U.S. Patents 2,566,245 and 2,566,263.
  • the emulsions can also be chemically sensitized with gold salts as described in Waller, Collins and Dodd U.S. Patent 2,399,083 or stabilized with gold salts as described in Damschroder U.S. Patent 2,597,856 and Yutzy and '2' Leermakers U.S. Patent 2,597,915.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazole methochloride.
  • the emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U.S. Patent 2,487,850), polyarnines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,- 925), or bis(fi-aminoethyl) sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926).
  • reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850), polyarnines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,- 925), or bis(fi-aminoethyl) sulfide and its water-soluble salts (Lowe and Jones U.S. Patent
  • the emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301; 1,846,302; and 1,942,- 854; White U.S. Patent 1,990,507; Brooker and White U.S. Patents 2,112,140; 2,165,338; 2,493,747; and 2,739,- 964; Brooker and Keyes U.S. Patent 2,493,748; Sprague U.S. Patents 2,503,776 and 2,519,001; Heseltine and Brooker U.S. Patent 2,666,761; Heseltine U.S. Patent 2,734,900; Van Lare U.S. Patent 2,739,149; and Kodak Limited British 450,958.
  • cyanine and merocyanine dyes such as those described in Brooker U.S. Patents 1,846,301; 1,846,302; and 1,942,- 854; White U.S. Patent 1,
  • the emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623; Carroll and Allen U.S. Patent 2,288,- 226; and Carroll and Spence U.S. Patent 2,334,864; and the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162.
  • Typical supports include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polyethylene film, polypropylene film, and related films of resinous materials, as well as paper, glass and others.
  • my emulsions are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support.
  • the support is coated in succession with a redsensitive layer, a green-sensitive layer and a blue-sensitive layer either with or without a Carey Lea filter layer between the blue-sensitive and green-sensitive layers.
  • the three differently color sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer.
  • these light-sensitive layers are arranged on the same side of the support.
  • Elements made for image transfer processing may use a separate reception sheet which is contacted with the i light-sensitive layer during its development or the reception layer may be an integral part of the light-sensitive element. Any of the support materials mentioned previously may be used for a separate reception sheet.
  • the reception layer comprises a hydrophilic colloid layer containing a cationic mordant, e.g., the polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk U.S. Patent 2,882,156, granted Apr. 14, 1959.
  • a cationic mordant e.g., the polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk U.S. Patent 2,882,156, granted Apr. 14, 1959.
  • Other mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al. U.S. Patent 2,484,430, granted Oct. 11, 1949, and cetyl trirnethyl ammonium bromide, etc.
  • Particularly effective mordanting compositions are described in copending applications of Kneckel et al. U.S. Ser. No.
  • EXAMPLE 2 Good magenta dye images are obtained by color developing light image exposed single layer gelatino-silver bromide emulsions containing my magenta-forming couplers No. 2 and No. 3 dissolved in coupler solvent, tri-ocresyl phosphate.
  • the coatings contain 400 mg. gelatin/ ft. mg. Ag/ft. 60 mg. of coupler/ft? and 30 mg. of solvent/K
  • the process and formula are as follows.
  • Acid stop bath 6.0 Formalin hardener 4.0 Water wash 4.0 Ferricyanide bleach 6.5 Water wash 4.0 Hypo fix i 4.5 Water wash 8.0
  • Acid stop bath Acetic acid (glacial) ml 8.6 Water to make, 1000.0 ml.
  • Formaline hardener Formalin (37% by weight formaldehyde in water) ml 20.00 Sodium bisulfite g 5.00 Borax g 3.82 Sodium hydroxide g 4.50 Water to make, 1000.00 ml.
  • F erricyanide bleach G Potassium ferricyanide 18.0 Sodium bromide 12.8 Borax 7.3 Boric acid 15.0
  • Examples 3, 4 and 5 will serve to illustrate the use of my cyan-forming couplers, but are not to limit the invention.
  • EXAMPLE 5 A good cyan dye image is obtained by color developing a light image exposed gelatino-silver bromide emulsion containing my cyan-forming coupler No. 9 dissolved in tri-o-cresylphosphate.
  • the coating contains 400 mg. gelatin/K 150 mg. Ag/ftF, 60 mg. coupler/ft. and mg. solvent/ft. The process is described in Example 2.
  • a good cyan dye image is produced by color developing a light image exposed emulsion containing my cyan-forming coupler No. 10.
  • This is a Fischer-type coupler and does not require coupler solvent for incorporating it in the emulsion.
  • the emulsion is like that described previously in this example except that no coupler solvent is used.
  • a light-image exposed emulsion containing cyan-forming coupler No. 8 instead of No. 10 produces a good diifusible cyan dye image when it is processed by contacting it for 7 minutes at 80 F. with a mordant containing receiving sheet that is presoaked in the following developer solution.
  • any of the other couplers of Formula I are prepared as coupler 1 starting in each instance with the appropriate four-equivalent parent 5-pyrazo1one coupler having the formula:
  • N CR4 where R and R are as defined previously, then proceeding with the synthesis to form the corresponding 4- diazonium-S-pyrazolone and reacting it with the appropriate organic acid and a-cylating agent.
  • Coupler 2 is prepared like coupler 1 by using 1 (2,4,6-trichlorophenyl)-3-(4-nitroanilino)-5-pyrazolone as the parent coupler and reacting the corresponding 4-diazonium-5-pyrazolone with stearic acid.
  • Coupler 3 is prepared like coupler 1 by using the parent coupler 1 (2,4,6 trichlorophenyl) 3- ⁇ 3-[ot-(2,4-di-tertamylphenoxy) acetamido]benzamido ⁇ -5-pyr-azolone and the acylating agent glacial acetic acid.
  • Coupler 7 A solution of 2 g. of intermediate B above in 100 ml. of ethyl acetate containing .1 g. of palladium on charcoal was reduced at 40 lb. p.s.i. hydrogen pressure, at room temperature. The solution was filtered, Washed twice with dilute sodium carbonate solution, dried, concentrated in vacuo, yielding the product.
  • Coupler 9 is prepared by the method used for coupler 6 by starting with the compound 1,4l-dihydroxy-N-[6- (2,4-di-tert-amylphenoxy)butyH-Z-naphthamide and then acylating it with acetic anhydride.
  • Couplers 4 (M.P. 162-164 C.), (MP. 6263 C.) and 6 (MP. 194 C.) were prepared by the synthesis described by Wilt and Johnson Ber. 26, 1910; Olcott, ].A.C.S. 59, 392 (1937), and Desai and Sethna J. Ind. Chem. Soc. 28, No. 4, 213-217 (1951), respectively.
  • Coupler 8 is prepared like coupler 6 by using stearoyl chloride in place of acetic anhydride as the acylating agent.
  • Coupler is prepared by reacting phenyl 1,4-di-hydroxy-Z-naphthoate (formed by reacting 1,4-di-hydroxy- 2-naphthoic acid with phenol) with N-(3,5-di-carbomethoxyphenyl)-N-s-tearylarnine to form 1,4-di-hydroxy- N-octadecyl-3,5'-dicarbomethoXy-2-naphthanilide which is hydrolyzed, then acetyl-ated with acetic anhydride to produce 1 hydroxy 4 acetoxy-N-octadecyl-3,5-di carboxy-Z-naphthanilide.
  • the two-equivalent image-forming couplers of my invention are distinguished from other two-equivalent couplers by having an acyloxy group substituted on the coupling position of the coupler molecule.
  • My nondiffusing couplers are dispersed readily in emulsion layers as a coupler solvent solution having a wide range of coupler to solvent ratios.
  • My couplers are not only valuable for the reasons cited but because photographic emulsion layers color developed with them require only /2 the amount of silver halide required by four-equivalent couplers. Of particular value are certain of my nondifi'using couplers which have high coupling reactivity when dispersed in photographic emulsion layers Without any high-boiling solvent. These couplers are coated to advantage in particularly thin layers that produce very sharp images.
  • a light-sensitive photographic element comprising a support and at least one light-sensitive layer comprising a hydrophilic colloid-silver halide emulsion having dispersed therein an unc-olored' dye image-forming twoand wherein R represents a group selected from the class consisting of an alkyl group having from 1 to 22 carbon atoms, a phenyl group, and a naphthyl group; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group and a heterocyclic group; R R R R R R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a carbonamido group, a sulfonamido group, a sulfamyl group and a carbamyl group; and W represents the nonmetallic atoms necessary to form a fused 5- or G-mem'
  • a light-sensitive photographic element comprising a support and at least one light-sensitive layer comprising a hydrophilic colloid-silver :halide emulsion having dispersed therein a magenta-forming two-equivalent coupler selected from those having the formula:
  • R represents a group selected from the class consisting of an alkyl group having from 1 to 22 carbon atoms, a phenyl group and a naphthyl group; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group and a heterocyclic group; and R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a carbonamido group, a sulfonamido group, a sulfamyl group, and a carbamyl group.
  • a light-sensitive photographic element comprising a support and at least one light-sensitive layer comprising a hydrophilic colloid-silver halide emulsion having dispersed therein a cyan-forming two-equivalent coupler selected from those having the formula:
  • R represents a group selected from the class consisting of an alkyl group having from 1 to 22 carbon atoms, a phenyl group and a naphthyl group
  • R R R R", R and R each represents a group selected from the class consisting of the hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a canbonamido group, a sulfonamido group, a sulfamyl group, and a carbamyl group
  • W represents the nonmetallic atoms necessary to form a fused 5- or 6-membered ring.
  • a light-sensitive photographic element of claim 1 comprising .a support, at least one hydrophilic-colloidsilver halide emulsion layer having dispersed therein a two-equivalent magenta image-forming coupler of Formula I and at least one hydrophilic-colloid-silver halide emulsion layer having dispersed therein a two-equivalent cyan image-forming coupler of Formula II.
  • a light-sensitive photographic element comprising a support, and a light-sensitive hydrophilic-colloid-silver halide emulsion layer having dispersed therein the twoequivalent coupler 1-(2,4,6-trichlonophenyl)-3-(4-nitroanilino)-4-stearoyloxy-S-pyrazolone.
  • a light-sensitive photographic element comprising a support, and a light-sensitive hydr-ophilic-colloid-silver halide emulsion layer having dispersed therein the twoequivalent coupler 1-(2,4,6-trichlorophenyl)-3- ⁇ 3-[a-(2,4- di-tert-amylphenoxy) acetamido]benzamido ⁇ -4-acetoxy- 5-pyrazolone.
  • a light-sensitive photographic element comprising a support, and a light-sensitive hydrophilic-colloid-silver halide emulsion layer having dispersed therein the tWoequivalent coupler 1 hydroxy-4-stearoyloxy-Z-naphthoic acid.
  • a light-sensitive photographic element comprising a support, and a light-sensitive hydrophiliocolloid-silver halide emulsion layer having dispersed therein the two- References Cited by the Examiner UNITED STATES PATENTS 2,436,130 2/1948 Weissberger et a1 96100 2,600,788 6/1952 Loria et al.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
US247302A 1962-12-26 1962-12-26 Two-equivalent couplers for color photography Expired - Lifetime US3311476A (en)

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Application Number Priority Date Filing Date Title
US247302A US3311476A (en) 1962-12-26 1962-12-26 Two-equivalent couplers for color photography
DEE26072A DE1181057B (de) 1962-12-26 1963-12-20 Farbkuppler fuer Purpur und Blaugruen enthaltendes photographisches Material
GB50607/63A GB1077873A (en) 1962-12-26 1963-12-23 Colour photography employing colour couplers
GB4871/67A GB1077875A (en) 1962-12-26 1963-12-23 Pyrazolone colour couplers
FR958168A FR1385697A (fr) 1962-12-26 1963-12-23 Nouveaux coupleurs chromogènes utilisables en photographie
BE641871A BE641871A (en:Method) 1962-12-26 1963-12-27
US584936A US3432521A (en) 1962-12-26 1966-08-10 4-acyloxy-5-pyrazolones

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Cited By (34)

* Cited by examiner, † Cited by third party
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US3415652A (en) * 1965-04-01 1968-12-10 Eastman Kodak Co Silver halide color photographic elements utilizing alpha-sulfonyloxy substituted two-equivalent yellow-forming couplers
US3419390A (en) * 1965-05-03 1968-12-31 Eastman Kodak Co Elements and developers for color photography utilizing phenolic couplers containingan aminoalkyl group on the coupling position
US3447928A (en) * 1965-07-26 1969-06-03 Eastman Kodak Co Silver halide emulsion containing twoequivalent yellow dye-forming coupler
US3458315A (en) * 1965-10-24 1969-07-29 Eastman Kodak Co Cyan couplers for color photography
US3617291A (en) * 1967-10-10 1971-11-02 Eastman Kodak Co Two-equivalent couplers for photography
DE2417945A1 (de) * 1973-04-13 1974-11-21 Fuji Photo Film Co Ltd Photographisches lichtempfindliches silberhalogenidmaterial
US4015988A (en) * 1974-03-04 1977-04-05 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive material
US4036643A (en) * 1973-06-11 1977-07-19 Gaf Corporation Diffusion transfer color process using lactone or sultone ring containing lipophilic non-diffusing color formers which yield diffusing dyes
US4191574A (en) * 1975-02-21 1980-03-04 Konishiroku Photo Industry Co., Ltd. Process for forming a photographic magenta dye image
US4221860A (en) * 1975-10-20 1980-09-09 Fuji Photo Film Co., Ltd. Process for forming color photographic images
US4237217A (en) * 1974-06-11 1980-12-02 Fuji Photo Film Co., Ltd. Silver halide emulsion containing two-equivalent magenta coupler
US4273861A (en) * 1973-06-19 1981-06-16 Fuji Photo Film Co., Ltd. Multilayer color photographic materials utilizing an interlayer correction coupler
US4330617A (en) * 1980-02-05 1982-05-18 Mitsubishi Paper Mills, Ltd. Photographic elements containing novel developing agent precursors
WO1982003131A1 (en) * 1981-03-02 1982-09-16 Corp Polaroid Cleavable polymers and photographic products and processes employing same
US4426444A (en) 1980-10-02 1984-01-17 Ciba Geigy Ag Hydroquinone derivatives and their use in photographic materials
US4446216A (en) * 1981-12-10 1984-05-01 Smith Norman A Photographic material
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
JPS59214030A (ja) * 1983-05-19 1984-12-03 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US4609620A (en) * 1982-03-11 1986-09-02 Ciba Geigy Ag Pyrazolone compounds and a process for their manufacture
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0202616A2 (en) 1985-05-16 1986-11-26 Konica Corporation Method for color-developing a silver halide photographic light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
US4770988A (en) * 1986-07-24 1988-09-13 Fuji Photo Film Co., Ltd. Silver halide color photographic material with combination of phenolic couplets
US4840883A (en) * 1987-06-26 1989-06-20 Konica Corporation Light-sensitive silver halide color photographic material containing novel cyan coupler
US4847185A (en) * 1988-06-30 1989-07-11 Eastman Kodak Company Photographic material and process (A)
US4857440A (en) * 1988-06-30 1989-08-15 Eastman Kodak Company Photographic material and process (B)
US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
EP0711804A2 (de) 1994-11-14 1996-05-15 Ciba-Geigy Ag Kryptolichtschutzmittel
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP2107122A1 (en) 2008-03-31 2009-10-07 FUJIFILM Corporation Protease detection material, set of protease detection materials, and method for measuring protease

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DE3432062A1 (de) * 1984-08-31 1986-03-06 Bayer Ag, 5090 Leverkusen Pyrazoldionderivate und ihre anwendung bei der bekaempfung von krankheiten

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US2436130A (en) * 1944-11-25 1948-02-17 Eastman Kodak Co Acyl substituted reactive methylene color couplers
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US2878263A (en) * 1958-02-14 1959-03-17 Ortho Pharma Corp 4-methyl-4-phenyl-5-pyrazolone
US2905694A (en) * 1959-09-22 Certain esters of i
US2933391A (en) * 1956-09-06 1960-04-19 Eastman Kodak Co Photographic emulsions containing 5-pyrazolone coupler compounds
CA602607A (en) * 1960-08-02 M. Mader Paul Photographic color reproduction process
US2983608A (en) * 1958-10-06 1961-05-09 Eastman Kodak Co Yellow-colored magenta-forming couplers
US3006759A (en) * 1959-08-03 1961-10-31 Eastman Kodak Co Two-equivalent magenta-forming couplers for color photography

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US2905694A (en) * 1959-09-22 Certain esters of i
CA602607A (en) * 1960-08-02 M. Mader Paul Photographic color reproduction process
US2436130A (en) * 1944-11-25 1948-02-17 Eastman Kodak Co Acyl substituted reactive methylene color couplers
US2600788A (en) * 1949-06-07 1952-06-17 Eastman Kodak Co Halogen-substituted pyrazolone couplers for color photography
US2933391A (en) * 1956-09-06 1960-04-19 Eastman Kodak Co Photographic emulsions containing 5-pyrazolone coupler compounds
US2878263A (en) * 1958-02-14 1959-03-17 Ortho Pharma Corp 4-methyl-4-phenyl-5-pyrazolone
US2983608A (en) * 1958-10-06 1961-05-09 Eastman Kodak Co Yellow-colored magenta-forming couplers
US3006759A (en) * 1959-08-03 1961-10-31 Eastman Kodak Co Two-equivalent magenta-forming couplers for color photography

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415652A (en) * 1965-04-01 1968-12-10 Eastman Kodak Co Silver halide color photographic elements utilizing alpha-sulfonyloxy substituted two-equivalent yellow-forming couplers
US3419390A (en) * 1965-05-03 1968-12-31 Eastman Kodak Co Elements and developers for color photography utilizing phenolic couplers containingan aminoalkyl group on the coupling position
US3447928A (en) * 1965-07-26 1969-06-03 Eastman Kodak Co Silver halide emulsion containing twoequivalent yellow dye-forming coupler
US3458315A (en) * 1965-10-24 1969-07-29 Eastman Kodak Co Cyan couplers for color photography
US3617291A (en) * 1967-10-10 1971-11-02 Eastman Kodak Co Two-equivalent couplers for photography
DE2417945A1 (de) * 1973-04-13 1974-11-21 Fuji Photo Film Co Ltd Photographisches lichtempfindliches silberhalogenidmaterial
US3926631A (en) * 1973-04-13 1975-12-16 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive material
US4036643A (en) * 1973-06-11 1977-07-19 Gaf Corporation Diffusion transfer color process using lactone or sultone ring containing lipophilic non-diffusing color formers which yield diffusing dyes
US4273861A (en) * 1973-06-19 1981-06-16 Fuji Photo Film Co., Ltd. Multilayer color photographic materials utilizing an interlayer correction coupler
US4015988A (en) * 1974-03-04 1977-04-05 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive material
US4237217A (en) * 1974-06-11 1980-12-02 Fuji Photo Film Co., Ltd. Silver halide emulsion containing two-equivalent magenta coupler
US4191574A (en) * 1975-02-21 1980-03-04 Konishiroku Photo Industry Co., Ltd. Process for forming a photographic magenta dye image
US4221860A (en) * 1975-10-20 1980-09-09 Fuji Photo Film Co., Ltd. Process for forming color photographic images
US4330617A (en) * 1980-02-05 1982-05-18 Mitsubishi Paper Mills, Ltd. Photographic elements containing novel developing agent precursors
US4426444A (en) 1980-10-02 1984-01-17 Ciba Geigy Ag Hydroquinone derivatives and their use in photographic materials
WO1982003131A1 (en) * 1981-03-02 1982-09-16 Corp Polaroid Cleavable polymers and photographic products and processes employing same
US4446216A (en) * 1981-12-10 1984-05-01 Smith Norman A Photographic material
US4609620A (en) * 1982-03-11 1986-09-02 Ciba Geigy Ag Pyrazolone compounds and a process for their manufacture
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
JPS59214030A (ja) * 1983-05-19 1984-12-03 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0202616A2 (en) 1985-05-16 1986-11-26 Konica Corporation Method for color-developing a silver halide photographic light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
US4770988A (en) * 1986-07-24 1988-09-13 Fuji Photo Film Co., Ltd. Silver halide color photographic material with combination of phenolic couplets
US4840883A (en) * 1987-06-26 1989-06-20 Konica Corporation Light-sensitive silver halide color photographic material containing novel cyan coupler
US4847185A (en) * 1988-06-30 1989-07-11 Eastman Kodak Company Photographic material and process (A)
US4857440A (en) * 1988-06-30 1989-08-15 Eastman Kodak Company Photographic material and process (B)
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
EP0711804A2 (de) 1994-11-14 1996-05-15 Ciba-Geigy Ag Kryptolichtschutzmittel
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP2107122A1 (en) 2008-03-31 2009-10-07 FUJIFILM Corporation Protease detection material, set of protease detection materials, and method for measuring protease

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GB1077875A (en) 1967-08-02
BE641871A (en:Method) 1964-06-29
DE1181057B (de) 1964-11-05

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