[go: up one dir, main page]

US2983608A - Yellow-colored magenta-forming couplers - Google Patents

Yellow-colored magenta-forming couplers Download PDF

Info

Publication number
US2983608A
US2983608A US765315A US76531558A US2983608A US 2983608 A US2983608 A US 2983608A US 765315 A US765315 A US 765315A US 76531558 A US76531558 A US 76531558A US 2983608 A US2983608 A US 2983608A
Authority
US
United States
Prior art keywords
coupler
yellow
couplers
magenta
colored
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US765315A
Inventor
Leo E Beavers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US765315A priority Critical patent/US2983608A/en
Priority to FR806824A priority patent/FR1238590A/en
Priority to GB33779/59A priority patent/GB937621A/en
Application granted granted Critical
Publication of US2983608A publication Critical patent/US2983608A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C7/32—Colour coupling substances
    • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
    • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore
    • 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

Definitions

  • Yellow-colored magenta-forming coupler compounds This invention relates to color photography and par- 15 made from colorless magenta-forming coupler compounds ticularly to colored color couplers for use in photographic that are incorporated in certain color negative materials processes. are insufliciently reactive to give the desired color correc- Color-forming compounds which react with the tive masking effects.
  • an development product of aromatic amino developing agents unwanted blue absorption of 0.28 density units is produced to form colored images upon photographic development by the magenta dye formed from the reaction of the are well known
  • these color-forming comoxidized primary aromatic amino developing agent with pounds of couplers are colorless or substantially colorthe uncolored magenta-forming Coupler A:
  • the coupler color Upon development of an emulsion layer containing one of these colored couplers, the coupler color is usually destroyed and a new color is formed by the coupling reaction of those points where development occurs.
  • Coupler B derived from uncolored coupler is insuificiently reactive V and a residual amount raises the blue absorption in the exposed area from 0.28 to 0.43 density units. Consequently, the colored Coupler B must be used in a con centration that is sufficient to give a density of 0.43 in unexposed regions. This situation prevails when the ratio of Coupler B to coupler incorporating solvent is 1:2. At the desired ratio of 12% the colored Coupler B is completely unreactive and gives no color correction.
  • an object of the present invention to provide a class of yellow-colored magenta-forming couplers for use with uncolored magenta-forming couplers to correct for the deficiencies in the magenta dye produced upon color development.
  • a further object is to provide a class of yellow-colored magenta-forming couplers which are sufiiciently reactive to give complete compensation for the unwanted blue absorption of the magenta dye produced upon colored development at the desired coupler to coupler incorporating solvent ratio of 11 /4
  • a still further object is to provide a yellow-colored magenta-forming coupler with a higher extinction co efficient than the available colored magenta-forming couplers.
  • a still further object is to provide a class of yellow-colored magenta-forming couplers which because of their superior characteristics can be used for color correction in color photographic products in thinner emulsion coatings to give a photographic product having a lower minimum density than would be possible with known colored magenta-forming couplers,
  • couplers of the 3-anilino-4-arylazo-5- pyrazolone type are valuable yellow-colored magentaforming couplers.
  • Our couplers are not only yellowcolored but are characterized by being completely reactive with the oxidized primary aromatic amino developing agents, even when used at a coupler to coupler incorporating solvent ratio of I:%.
  • our Coupler I is completely reactive at a coupler to coupler incorporating solvent ratio of 12% and gives complete compensation for the unwanted blue absorption of the magenta dye when incorporated in sufficient amount to have the density of 0.28 units to blue light.
  • Coupler I has an extinction co-efiicient of 2.8 in butyl acetate as compared to an extinction coefiicient of 1.5 X 10 in butyl acetate given by Coupler B.
  • couplers give their user valuable advantages over one using the yellow-colored magenta-forming coupler compounds known before. For example, smaller amounts of our coupler can be used than similar couplers outside the invention. In addition to this, the products in which our couplers are used are improved because they have a lower minimum emulsion layers. Thinner emulsion layers are often desirably employed for giving images with improved definition and resolution.
  • R is an aryl group such as a phenyl radical or a phenyl radical substituted at the 2,4, and 6 carbons with halogen atoms, such as a 2,4,6-trichlorophenyl, a 2,4,6- tribromophenyl, a 2,4,6-triiodophenyl or a 2,4,6-trifiuorophenyl group;
  • R is a hydrogen atom or an alkyl group having from 1-8 carbon atoms but preferably from 1-4 carbon atoms;
  • X, Y and Z are hydrogen atoms and alkyl radicals usually having from l20 carbon atoms but preferably 1-15 with at least one of the substituents X, Y and Z being an alkyl radical;
  • R" is a hydrogen atom, an alkyl or an alkoxy radical usually having from 1-10 carbon atoms but preferably from 1-6 carbon atoms.
  • this invention also includes compounds of the above formula wherein R is a phenyl group substituted at the 2, 4, and 6 carbons with alkyl or alkoxy radicals usually having from l-6 carbon atoms, aryl groups, aryloxy groups, cyano groups, carbalkoxy groups, or nitro groups; and where R is an acylamido group, a carbalkoxy group, a dialkylamino group, an arylether group or other electron-donating substituent.
  • 317 g. (1.5 moles) of 2,4,6-trichlorophenylhyg H drazine 249 g. (1.65 moles) of ethyl fi-ethoxy-;8-imino- N propionate, 950 cc. of absolute ethanol, and 5 cc. of
  • alkaline solution is refluxed 1 hour, diluted with l 1. of
  • R' represent the groups defined above. melting at 222-224.
  • Concentration of the liquors to A Typical compounds embodying the invention and which volume and dilution with 500 cc. of Water gives 51 g. of can be used according to the invention include the folpink solid melting at 2l8220.
  • Step 2.l (2',4,6'-trichlorophenyl)-3(4"-nitropheninvention is not limited: oxy)acetarnido-5-pyrazolone is prepared by the reaction COUPLER I O 02H; 01 r g 1 (22426 trlchlorophenyl) 3 ⁇ 4" [a(2"',4"' d1 tertiaryamylphenoxy) butyramidoJanfllno ⁇ 4 (4""methoxyphenyl) azo-5-pyrazo1one [Melting point, 218.5-221 0.] (I?
  • Coupler I A typical process for preparing Coupler I is as follows: q d 0 .7 I Procedure aminoanilino)--pyrazolone is prepared by the reaction- Compound D+3Hr-- A 500-m1. 3-necked flask is equipped with a stirrer, C1 dropping funnel and water-cooled condenser. The flask 5 i is charged with 55.6 g. (.2 mole) of 1-(2,4,6-trichloro- +2H 0 phenyl)-3-amino-5-pyrazolone, and 200 ml. of dry ace- ()1 1 2 tonitrile and heated at reflux over a steam bath with O mechanical stirring. A solution of 47 g.
  • amylphenoxy)butyrlino)-5-pyrazolone is prepared by the reactionamido]anilino ⁇ -5-pyrazolone is made by the reaction 0 CzHs
  • Compound E+CI(I(IJH-O CsHn(t)- C H t a 11() Cl 0 02H /N C-NH NHC--CH-O 0.11110) C l cm (a Compound]? Compound O+Na0 H---- Procedure A mixture of 5.7 g. 0.154 mole) of 1-(2',4',6'-tri; 01 chlorophenyl)-3 (4" aminoanilino) 5 pyrazolone and 5.23 g.
  • Coupler VI is prepared by the procedure described Couplers II, III, IV and V are prepared according to the procedure described for Coupler I excepting that Compound F is reacted in Step 6 with the appropriate for the Coupler I synthesis.
  • COUPLER vn 1 (25456 trichlorophenyl) s 4" mz'" 4'" 11- terondary amylphenyl)azo diazonium chloride compound as shown in the following [Melting point, 144.148. 0.]
  • Coupler VII is prepared by the procedure described for Coupler I excepting that Compound F is reacted in Step 6 with 4-secondary amyl benzene diazonium chloride.
  • Our yellow-colored magenta-forming coupler compounds can be used in any photographic emulsion where magenta-forming couplers are used or can be used. Usually these couplers are used in admixture with uncolored magenta-forming couplers. Colored and uncolored couplers are selected which form either the same magenta dye upon color development or a magenta dye of the same hue. These photographic emulsions producing color corrected magenta images can be used alone, however, they are usually used in combination with photographic elements forming a yellow image, and a cyan or corrected cyan image to produce a colored picture.
  • EXAMPLE I 0.25 gram of our yellow-colored magenta-forming Coupler I and 0.25 gram of the uncolored magentaforming coupler 1(2,4',6'-trichlorophenyl)-3[3"-(2", 4"'-diamylphenoxyacetamido) benzamidoJ-S-pyrazolone were dissolved in 1 gram of tri-o-cresyl phosphate with stirring at 110 C. This solution was intimately mixed with and dispersed in a solution containing 22 ml. of 10% gelatin and 2 ml. of .5% Alkanol B. 2 ml. of 7.5% saponin and 15 ml. of water were added to this dispersion. 25 ml. of this dispersion was added to ml. of a medium speed silver bromoiodide emulsion and this was coated on a cellulose acetate support and dried.
  • the coating was given an image exposure and developed in an alkaline developer solution containing 2- amino-S-(N-ethyl-N-B-methane sulfonamidoethyl)toluene sulfate, to form a negative silver and magenta dye image and a yellow-positive dye image.
  • the silver image and the residual silver halide were removed by treating film in a ferri cyanide bleach followed by hypo fix. This left a negative image in magenta dye having maximum absorption at a wavelength of 534 mg, and a positive image in residual yellow-colored coupler having a maximum absorption at 430 mu.
  • the couplers of our invention are used in photographic emulsions of the developing out type.
  • the emulsions 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.
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and Sodium chloropalladite, which are used for sensitiz- 14 ing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, and as antiioggants 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 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), polyamines, 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(5-aminoethyl) sulfide and its watersoluble salts (Lowe and Jones U.S. Patent 2,521,926).
  • reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850), polyamines, 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(5-aminoethyl) sulfide and its watersoluble salts (Lowe and Jones U.S. Patent 2,521,926).
  • 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; Hesseltiue U.S. Patent 2,734,900; VanLare 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
  • the emulsions can also be stabilized with the mercury compounds of Allen, Byers, and Murray U.S. Patent 2,728,663; Carroll and Murray U.S. Patent 2,728,664, and Leubner and Murray U.S. Patent 2,728,665; the triazoles of Heimbach and Kelly U.S. Patent 2,444,608; the azaindenes of Heimbach and Kelly U.S. Patents 2,444,605 and 2,444,606; Heimbach U.S. Patents 2,444,- 607 and 2,450,397; Heimbach and Clark U.S. Patent 2,444,609; Allen and Reynolds U.S. Patents 2,713,541 and 2,743,181; Carroll and Beach U.S.
  • Patent 2,716,062 Allen and Beilfuss U.S. Patent 2,735,769; Reynolds and Sagal U.S. Patent 2,756,147; Allen and Sagura U.S. Patent 2,772,164, and those disclosed by Birr in the Z. wiss. Phot. 47, 2(1952); the quaternary b-enzothiazolium compounds of Brooker and Stand U.S. Patent 2,131,038; and the zinc and cadmium salts of Jones U.S. Patent 2,839,405.
  • 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.
  • the emulsions may contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5-pentane diol as described in U.S. application Serial No. 588,951 of Milton and Murray; an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in U.S. application Serial No. 662,564 of Milton; bis-(ethoxy diethylene glycol) succinate as described in Gray U.S.
  • a suitable gelatin plasticizer such as glycerin
  • a dihydroxy alkane such as 1,5-pentane diol as described in U.S. application Serial No. 588,951 of Milton and Murray
  • an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in U.S. application Serial No. 662,564 of Milton
  • bis-(ethoxy diethylene glycol) succinate as described in Gray U.S.
  • Patent 2,940,854 or a polymeric hydrosol as results from the emulsion polymerization of a mixture of an amide of an acid of the acrylic acid series, an acrylic acid ester and a styrene-type compound as described in Long U.S. Patent 2,852,386.
  • the plasticizer may be added to the emulsion before or after the addition of a sensitizing dye, if used.
  • the emulsion may be hardened with any suitable hardener for gelatin such as formaldehyde; a halogensubstituted aliphatic acid such as mucobromic acid as described in U.S. Patent 2,080,019 of White; a compound having a plurality of acid anhydride groups such as 7,8- diphenylbicyclo(2,2,2)-7-octene 2,3,5,6 tetracarboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-
  • any suitable hardener for gelatin such as formaldehyde
  • a halogensubstituted aliphatic acid such as mucobromic acid as described in U.S. Patent 2,080,019 of White
  • a compound having a plurality of acid anhydride groups such as 7,8- diphenylbicyclo(2,2,2)-7-octene 2,
  • disulfonyl chloride as described in U.S. Patents 2,725,- 294 and 2,725,295 of Allen and Carroll; a cyclic 1,2- diketone such as cyclopentane-1,2-dione as described in U.S. Patent 2,725,305 of Allen and Byers; a bisestcr of methane-sulfonic acid such as 1,2-di-(methanesulfonoxy)- ethane as described in U.S. Patent 2,726,162 of Allen and Laakso; 1,3-dihydroxymethylbenzimidazole-2-one as described in U.S.
  • Patent 2,732,316 of July, Knott and Pollak a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms such as B-methyl glutaraldehyde bissodium bisulfite as described in U.S. application Serial No. 556,031 of Allen and Burness; a bis-aziridine carboxamide such as trirnethylene bis(1-aziridine carboxamide) as described in U.S. application Serial No. 599,- 891 of Allen and Webster; or 2,3-dihydroxy dioxane as described in Jefireys U.S. Patent 2,870,013.
  • a dialdehyde or a sodium bisulfite derivative thereof the aldehyde groups of which are separated by 2-3 carbon atoms
  • B-methyl glutaraldehyde bissodium bisulfite as described in U.S. application Serial No. 556,031 of Allen and Burness
  • the emulsions may have been supplied with a coating aid such as saponin; a lauryl or oleyl monoether of polyethylene glycol as described in U.S. Patent 2,831,766 of Knox and Davis; a salt of a sulfated and alkylated polyethylene glycol ether as described in U.S. Patent 2,719,- 087 of Knox and Davis; an acylated alkyl taurine such as the sodium salt of N-oleoyl-N-methyl taurine as described in U.S.
  • a coating aid such as saponin
  • a lauryl or oleyl monoether of polyethylene glycol as described in U.S. Patent 2,831,766 of Knox and Davis
  • a salt of a sulfated and alkylated polyethylene glycol ether as described in U.S. Patent 2,719,- 087 of Knox and Davis
  • an acylated alkyl taurine such as the sodium salt of N-oleoyl-N-methyl tau
  • Patent 2,739,891 of Knox, Twardokus, and Davis the reaction product of a dianhydride of tetracarboxybutane with an alcohol or an aliphatic amine containing from 8 to 18 carbon atoms which is treated with a base, for example, the sodium salt of the monoester of tetracarboxybutane as described in Knox, Stenberg, and Wilson U.S. Patent 2,843,487; a water-soluble maleopimarate or a mixture of a Water-soluble maleopimarate and a substituted glutamate salt as described in U.S.
  • Patent 2,823,123 of Knox and Fowler an alkali metal salt of a substituted amino acid such as disodium N- (carbo-p-tert.octylphenoxypentaethoxy) glutamate as described in U.S. application Serial No. 600,679 of Knox and Wilson; or a sulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate or N-lauryl disodium sulfosuccinamate as described in U.S. application Serial No. 691,125 of Knox and Stenbcrg.
  • a substituted amino acid such as disodium N- (carbo-p-tert.octylphenoxypentaethoxy) glutamate as described in U.S. application Serial No. 600,679 of Knox and Wilson
  • a sulfosuccinamate
  • the couplers which we have described may be used in various kinds of photographic emulsions.
  • Various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • the couplers can be used in emulsions of the mixed-packet type, such as described in Godowsky U.S. Patent 2,696,794 or emulsions of the mixed-grain type, such as described in Carroll and Hanson U.S. Patent 2,592,243.
  • These agents can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly inside the silver halide crystal, such as those described in Davey and Knott U.S. Patent 2,592,250.
  • gelatin In the preparation of the silver halide dispersions employed for preparing silver halide emulsions there may be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
  • colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
  • 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 19-26% 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 025-15 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 cyanoacetate 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 Illingsworth, Dann, and Gates U.S. Patent 2,852,382.
  • compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide in its preparation.
  • Photographic emulsions containing our couplers may be coated on transparent supports such as glass, cellulose esters, or on a non-transparent reflecting material such as paper or opaque cellulose ester.
  • Our yellow-colored magenta-forming 3-anilino-4-ary1- azo-5-pyrazolone couplers described hereinabove are superior to the colored magenta-forming couplers known and used before to correct the undesired blue absorption of the magenta dye formed upon color development. They are characterized by being completely reactive with oxidized primary aromatic amino developing agents when they are used in emulsion dispersions having a coupler to coupler incorporating solvent ratio of 1: 4 and give complete compensation for unwanted blue absorption of the magenta dye when incorporated in the proper amount.
  • R is a member selected from the group consisting of a phenyl radical and halogen substituted phenyl radicals
  • R is a member selected from the group consisting of hydrogen atoms and alkyl radicals having l to 4 carbon atoms
  • X, Y, and Z are selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 20 carbon atoms and where at least one of the substituents X, Y, and Z is said alkyl radical
  • R" is selected from the group consisting of alkyl radicals having 1 to carbon atoms and alkoxy radicals having 1 to 10 carbon atoms, and an uncolored magenta-forming pyrazolone coupler which forms a dye of the same hue as formed by the yellow-colored magenta-forming coupler upon coupling with an oxidized primary aromatic amino developing agent.
  • R is a member selected from the group consisting of a phenyl radical and halogen substituted phenyl radicals
  • R is a member selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 4 carbon atoms
  • X, Y, and Z are selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 20 carbon atoms and where at least one of the substituents X, Y, and Z is said alkyl radical
  • R" is selected from the group consisting of alkyl radicals having from 1 to 10 carbon atoms and alkoxy radicals having 1 to 10 carbon atoms, and (2) an uncolored magentaforming coupler which both form the same magenta dye, said uncolored coupler having the formula:
  • R is a member selected from the group consisting of phenyl radicals and halogen substituted phenyl radicals
  • R is a member selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 4 carbon atoms
  • X, Y and Z are selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 20 carbon atoms and where at least one of the substituents X, Y, and Z is said alkyl radical
  • R" is selected from the group consisting of alkyl radicals 18 having from 1 to 10 carbon atoms and alkoxy radicals having from 1 to 10 carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Developing Agents For Electrophotography (AREA)

Description

Patented May 9, 1961 United States Patent There is formed in this way a dye image consisting of the new dye and the residual colored coupler. The
2,983,608 theory of color correction requires that the absorption of p the residual colored coupler and the undesired absorp- E%%%%EE 5 tion of the image dye should be constant. This requirement is not always fulfilled by colored couplers in use Leo E. Beavers, Rochester, N.Y., assignor to Eastman so errors are introduced in the process of color Kodak Company, Rochester, N.Y., a corporation of correction New Jersey Magenta dyes produced upon color development have an undesired absorption of light in the blue region of No Drawmg' Filed 1958 set. 765,315 the spectrum. Therefore, it is desirable to have yellow- 13 Claims. (Cl. 96-100) colored magenta-forming coupler compounds that can be used to correct for this unwanted blue absorption.
Yellow-colored magenta-forming coupler compounds This invention relates to color photography and par- 15 made from colorless magenta-forming coupler compounds ticularly to colored color couplers for use in photographic that are incorporated in certain color negative materials processes. are insufliciently reactive to give the desired color correc- Color-forming compounds which react with the tive masking effects. For example, in a typical case, an development product of aromatic amino developing agents unwanted blue absorption of 0.28 density units is produced to form colored images upon photographic development by the magenta dye formed from the reaction of the are well known, Generally these color-forming comoxidized primary aromatic amino developing agent with pounds of couplers are colorless or substantially colorthe uncolored magenta-forming Coupler A:
1 (2,4,6'-trichlorophenyl) -3 [3" (2",4"'-di-amylpheuoxyacetamido) benzamido] -5-pyrazo1one less. This lack of color is usually desirable when the In an ideal situation enough blue absorbing colored coupler is to be incorporated in the emulsion layer and coupler is mixed with the colorless coupler to compensate the unused coupler remains after formation of the colored for this unwanted absorption as described in Vittum and image, Arnold, US. Patent 2,428,054 and Hansen, US. Patent Couplers which are in themselves more or less strongly 2,449,966. However, the yellow-colored magenta-formcolored and which contain a chromophore group which ing Coupler B:
o 01 H N=CNHO 0 01 l Nnii on 0 o H 1 on H Q u g 1R- EH11 1(2',4',6'-triehlorophenyl -3 [3"-(2"',4" '-di-amylphenoxyacetamido) benzamido] -4-( -n1ethoxyphenylazo) -5-pyrazolone is split off or destroyed during and by means of the coupling reaction with the result that the original color of the coupler is destroyed and a new dye is formed upon coupling are disclosed in Glass, 2,455,170, Hansen, 2,449,966, and Heimbaeh et al. 2,688,539.
Upon development of an emulsion layer containing one of these colored couplers, the coupler color is usually destroyed and a new color is formed by the coupling reaction of those points where development occurs.
derived from uncolored coupler is insuificiently reactive V and a residual amount raises the blue absorption in the exposed area from 0.28 to 0.43 density units. Consequently, the colored Coupler B must be used in a con centration that is sufficient to give a density of 0.43 in unexposed regions. This situation prevails when the ratio of Coupler B to coupler incorporating solvent is 1:2. At the desired ratio of 12% the colored Coupler B is completely unreactive and gives no color correction.
Furthermore, it is desired to have yellow-colored magenta-forming couplers with higher extinction coefficients than the available colored couplers.
It is, therefore, an object of the present invention to provide a class of yellow-colored magenta-forming couplers for use with uncolored magenta-forming couplers to correct for the deficiencies in the magenta dye produced upon color development. A further object is to provide a class of yellow-colored magenta-forming couplers which are sufiiciently reactive to give complete compensation for the unwanted blue absorption of the magenta dye produced upon colored development at the desired coupler to coupler incorporating solvent ratio of 11 /4 A still further object is to provide a yellow-colored magenta-forming coupler with a higher extinction co efficient than the available colored magenta-forming couplers. A still further object is to provide a class of yellow-colored magenta-forming couplers which because of their superior characteristics can be used for color correction in color photographic products in thinner emulsion coatings to give a photographic product having a lower minimum density than would be possible with known colored magenta-forming couplers, Other objects will appear from the following description and claims.
These and other objects are accomplished by means of this invention as described hereinafter. We have discovered that couplers of the 3-anilino-4-arylazo-5- pyrazolone type are valuable yellow-colored magentaforming couplers. Our couplers are not only yellowcolored but are characterized by being completely reactive with the oxidized primary aromatic amino developing agents, even when used at a coupler to coupler incorporating solvent ratio of I:%. For example, our Coupler I is completely reactive at a coupler to coupler incorporating solvent ratio of 12% and gives complete compensation for the unwanted blue absorption of the magenta dye when incorporated in sufficient amount to have the density of 0.28 units to blue light. These characteristics are entirely unexpected because of the vary small chemical differences between our Coupler I and Coupler B which is completely unreactive at coupler to coupler incorporating solvent ratios of 1:% and therefore gives no color correction.
Our couplers are not only valuable because of their reactivity but because they have higher extinction co-efiicients than do the corresponding 3-benzamido-5-pyrazolone type of coupler. For example, our Coupler I has an extinction co-efiicient of 2.8 in butyl acetate as compared to an extinction coefiicient of 1.5 X 10 in butyl acetate given by Coupler B.
The characteristics shown by our couplers give their user valuable advantages over one using the yellow-colored magenta-forming coupler compounds known before. For example, smaller amounts of our coupler can be used than similar couplers outside the invention. In addition to this, the products in which our couplers are used are improved because they have a lower minimum emulsion layers. Thinner emulsion layers are often desirably employed for giving images with improved definition and resolution.
The preferred embodiments of this invention have the wherein R is an aryl group such as a phenyl radical or a phenyl radical substituted at the 2,4, and 6 carbons with halogen atoms, such as a 2,4,6-trichlorophenyl, a 2,4,6- tribromophenyl, a 2,4,6-triiodophenyl or a 2,4,6-trifiuorophenyl group; R is a hydrogen atom or an alkyl group having from 1-8 carbon atoms but preferably from 1-4 carbon atoms; X, Y and Z are hydrogen atoms and alkyl radicals usually having from l20 carbon atoms but preferably 1-15 with at least one of the substituents X, Y and Z being an alkyl radical; R" is a hydrogen atom, an alkyl or an alkoxy radical usually having from 1-10 carbon atoms but preferably from 1-6 carbon atoms.
In addition to the preferred embodiments defined above, this invention also includes compounds of the above formula wherein R is a phenyl group substituted at the 2, 4, and 6 carbons with alkyl or alkoxy radicals usually having from l-6 carbon atoms, aryl groups, aryloxy groups, cyano groups, carbalkoxy groups, or nitro groups; and where R is an acylamido group, a carbalkoxy group, a dialkylamino group, an arylether group or other electron-donating substituent.
The yellow color of our couplers is destroyed upon reaction with an oxidized primary aromatic amino developing agent and a magenta-colored dye is formed. Although the exact mechanism of this reaction is not completely understood, it appears as though the reaction may proceed as follows:
N=G-R'" Step 1.1-(2,4,6 trichlorophenyl) -3-a.mino-5-pyrazo- Q l lone is prepared by the reaction A) I 5 o-GaHs 0 NaOCzH; Cl- NHNHz-I- HCHMJ 1 NH OCgHs C1 T /l\=C-NH HzC-N-CH; 01- N\ 1 o: H N wherein R represents the groups described by the gen- 8 eral formula and R represents the groups described as Ompmmd A being substituted on the carbon atom in the 3 position of the S-pyrazolone of the general formula. The compounds of this invention can be used in ad- 01 mixture with the uneolored couplers which appear to g /N=C-NH: react as fOllOWSi 2O CompoundA-i-OEhO -)Cl N\ +oH3o H 0- H2 Na Q l Compound B Procedure N=CR Q 39 In a 5-1. flask equipped with a reflux condenser is placed 317 g. (1.5 moles) of 2,4,6-trichlorophenylhyg H drazine, 249 g. (1.65 moles) of ethyl fi-ethoxy-;8-imino- N propionate, 950 cc. of absolute ethanol, and 5 cc. of
glacial acetic acid. The reaction is refluxed 2.5 hours.
Meanwhile, 69 g. (3.0 moles) of sodium is reacted with 1100 cc. of absolute ethanol and added cautiously through the condenser after the original reflux. The
alkaline solution is refluxed 1 hour, diluted with l 1. of
HBCN'OH3 warm water, acidified with 190 cc. of glacial acetic acid, 40 and cooled to 5. The solid is filtered, Washed with cold water and dried. The yield is 317 g. of pink crystals,
wherein R' represent the groups defined above. melting at 222-224". Concentration of the liquors to A Typical compounds embodying the invention and which volume and dilution with 500 cc. of Water gives 51 g. of can be used according to the invention include the folpink solid melting at 2l8220. lowing which illustrate the invention but to which the Step 2.l (2',4,6'-trichlorophenyl)-3(4"-nitropheninvention is not limited: oxy)acetarnido-5-pyrazolone is prepared by the reaction COUPLER I O 02H; 01 r g 1 (22426 trlchlorophenyl) 3 {4" [a(2"',4"' d1 tertiaryamylphenoxy) butyramidoJanfllno} 4 (4""methoxyphenyl) azo-5-pyrazo1one [Melting point, 218.5-221 0.] (I? A t 1 cetoni ri e CompoundB+C10GHz-O N0 Percent Composition Calculated Found h t 01 ll 2. &3 6.3 N=o-NHo-oH,-0 N 10. 4 11.1 or 13.1 11.3
C-CH:
A typical process for preparing Coupler I is as follows: q d 0 .7 I Procedure aminoanilino)--pyrazolone is prepared by the reaction- Compound D+3Hr-- A 500-m1. 3-necked flask is equipped with a stirrer, C1 dropping funnel and water-cooled condenser. The flask 5 i is charged with 55.6 g. (.2 mole) of 1-(2,4,6-trichloro- +2H 0 phenyl)-3-amino-5-pyrazolone, and 200 ml. of dry ace- ()1 1 2 tonitrile and heated at reflux over a steam bath with O mechanical stirring. A solution of 47 g. (.2 mole) of or: CmpmmdE (p-nitrophenoxy)acetyl chloride, in 100 ml. of dry aceprocedure tonitrile is added from the dropping funnel in mm. Solution is complete at this point, but soon a precipitate A solution of 1 0 g (0.025 mole) of 1-(2',4',6'-tr1- starts to form. After 4 hours the precepitate is filtered P YD -PY 200 from the hot mixture, and washed on the funnel first with 1 cc. of alcholo 1s hydrogenated for 3 hours at 40 p.s.1. and 100 ml. of fresh acetonitrile and then with about 2 liters 40 The catalyst 13 filtered 0E and fiitrate .concentrat' f Water The crude 6, trichlomphenyl) 3 [w ed to 50 cc. under vacuum. The solid is redissolved on O heating then separated on coohng givlng 5.1 g. of 1-(2', (4 -n1trophenoxy)acetam1do]-5-pyrazo1one1 s crystall zed 4l,6l trichlorophenyl) 3 (4 aminoanflin0) 5 pyrazolone from 90 percent acetic acid (50 ml./g.) to give a purified 20 with avMp of Product meltlllg at Step 5. From this compound 1-(2',4',6'-t1ichloro- Step 3. 1-(2',4',6'-trichlorophenyl)-3-(4"-nitroaniphenyl) 3 {4"[a-(2",4"'-di-tert. amylphenoxy)butyrlino)-5-pyrazolone is prepared by the reactionamido]anilino}-5-pyrazolone is made by the reaction 0 CzHs Compound E+CI(I(IJH-O CsHn(t)- C H t a 11() Cl 0 02H /N=C-NH NHC--CH-O 0.11110) C l cm (a Compound]? Compound O+Na0 H---- Procedure A mixture of 5.7 g. 0.154 mole) of 1-(2',4',6'-tri; 01 chlorophenyl)-3 (4" aminoanilino) 5 pyrazolone and 5.23 g. (0.154 mole) of a-(2,4-di-tertiaryamylphenoxy) O-CH2 butyryl chloride in 250 cc. of acetonitrile is refluxed for 01 ll 0 7 /2 hours then allowed to-stand for 16 hours followed by Com 01m (113 2 hours additional refluxing. The reaction mixture is p evaporated to dryness in vacuo. The residue is dissolved in 25 cc. of acetone and 200 cc. of hexane (from petroleum) is added. The mixture is digested in a steam Procedure bath until crystallization occurs. On cooling the crude product separates. Alternating recrystallization from A 12-1it fl k equipped ith a me hani al tirrer is acetone-hexane and from acetonitn'le gives 6.0 g. of tiny charged with 840 cc. of water, 3.2 l. of 3-A alcohol and Whlte crystals meltlngfit 352 g. (8.8 moles) of freshly opened sodium hydroxide Step 6- COUPler I is made by the (c.p.). The solution formed on stirring is cooled to room temperature and 2 Kg (4.38 moles) of 1-(2,4,6'-triou d F+0 a0-Ni01 Gou 1erI chlorophenyl)-3-[m-(4"-nitrophenoxy)acetamido] 5 pyrafomnefs i After bemg smied Overmght the To asolution of 1.34 g. 0.002 mole) of 1-(2,4',6-trireaction nuxture 1s filtered and the SOild washed on the chlorophenyl) 3 (2!n di tertiar am funnel with 3-A alcohol unit most of the red color is y y w h d out The combined filtrate and Washin s are phenoxy)-butyramido]an111no}-5-pyrazolone in 27 cc. of as d I 1 id th Odu t I pyridine is added during /2 hour at 05 to the theoretii s 128 f aclal ace 2 e r S cal amount of diazotized 4-methoxyaniline. The mixture ecte on a app mme was 6 W1 ace 10 an is stirred for 3 hours then drowned in ice and water to dried. This crude product is recrystallized by dissolving in 3 l. of warm N,N-dimethylformamide and adding 30 l. of 3-A alcohol at room temperature, yielding 1240 g. with a M.P. of 299-304.
give 1.6 g. of crude product. This solid is crystallized twice from acetonitrile giving 0.6 g. of l-(2',4',6'-trichlorophenyl) 3 {4" [a(2"',4' di tertiaryamylphenoxy) butyramido] anilino}-4-( 4 methoxyphenyl) azo Step 4. 1 (2',4',6' trichlorophenyl) 3 (4" S-pyrazolone, with a M.P. of 218.5- -221 C.
NHC-CH-O Cl N lHn (t) IL it 1 (2',4',=6' trlchlorophenyl) 3 {4 [a(2",4"' di tertiaryamylphenoxy)butyramido]aniline} 4 (4"" dodecoxyphenyDazo-Ei-pyrazolone [Melting point, 98.-102. (3.]
[Melting point, 166.-168.) 0.]
Percent Composition Calculated Found Pereent Composition Calculated Found (J 66.3 66.7 0.. 71.7 71.4 7. 3 7. 3 H 7.1 7. 0 N. 8. 8 9. 3 N 12.0 12. 2 O] 11.1 1L0 0... 9.1 9.6
Coupler VI is prepared by the procedure described Couplers II, III, IV and V are prepared according to the procedure described for Coupler I excepting that Compound F is reacted in Step 6 with the appropriate for the Coupler I synthesis.
COUPLER vn 1 (25456 trichlorophenyl) s 4" mz'" 4'" 11- terondary amylphenyl)azo diazonium chloride compound as shown in the following [Melting point, 144.148. 0.]
for Coupler I except that in Step 1 phenyl hydrazine is used in place of the 2,4,6-trichlorophenylhydrazine used N=I -NH NHC- 11-0 CaHMt) table:
Coupler Diazonium Chloride Used in Step 6 of Synthesis Percent Composition Calculated Found 4-ethoxy benzene diazonium chloride. C. 65. 5 65. 3 2-ethoxy benzene diazonium chloride. FT 6. 6 6. 5 4-butoxy benzene diazonium chloride. N. 10.0 10. 3 4-dodeeoxy benzene diazonium chloride. C 12. 6 12.8
COUPLER VI 0 CaHn CHa Coupler VII is prepared by the procedure described for Coupler I excepting that Compound F is reacted in Step 6 with 4-secondary amyl benzene diazonium chloride.
Our yellow-colored magenta-forming coupler compounds can be used in any photographic emulsion where magenta-forming couplers are used or can be used. Usually these couplers are used in admixture with uncolored magenta-forming couplers. Colored and uncolored couplers are selected which form either the same magenta dye upon color development or a magenta dye of the same hue. These photographic emulsions producing color corrected magenta images can be used alone, however, they are usually used in combination with photographic elements forming a yellow image, and a cyan or corrected cyan image to produce a colored picture.
The following examples illustrate a typical way in which our couplers can be incorporated and used in color photographic material:
EXAMPLE I 0.25 gram of our yellow-colored magenta-forming Coupler I and 0.25 gram of the uncolored magentaforming coupler 1(2,4',6'-trichlorophenyl)-3[3"-(2", 4"'-diamylphenoxyacetamido) benzamidoJ-S-pyrazolone were dissolved in 1 gram of tri-o-cresyl phosphate with stirring at 110 C. This solution was intimately mixed with and dispersed in a solution containing 22 ml. of 10% gelatin and 2 ml. of .5% Alkanol B. 2 ml. of 7.5% saponin and 15 ml. of water were added to this dispersion. 25 ml. of this dispersion was added to ml. of a medium speed silver bromoiodide emulsion and this was coated on a cellulose acetate support and dried.
The coating was given an image exposure and developed in an alkaline developer solution containing 2- amino-S-(N-ethyl-N-B-methane sulfonamidoethyl)toluene sulfate, to form a negative silver and magenta dye image and a yellow-positive dye image. The silver image and the residual silver halide were removed by treating film in a ferri cyanide bleach followed by hypo fix. This left a negative image in magenta dye having maximum absorption at a wavelength of 534 mg, and a positive image in residual yellow-colored coupler having a maximum absorption at 430 mu.
EXAMPLE II Similar results were obtained by using a dispersion made by dissolving 0.25 gram of our yellow-colored magenta-forming Coupler I and 0.25 gram of the uncolored magenta-forming coupler 1(2',4',6'-trichloro phenyl) 3 [3-(2",4"'-diamylphenoxyacetamido)- benzamido]-5-pyrazolone in 0.125 gram of tri-o-cresyl phosphate and 4 ml. of ethyl acetate. This solution was added to the same amount of gelatin solution and the emulsion as in Example I, and coated in the same manner. The ethyl acetate evaporated from the coating on drying. The same exposure and processing conditions yielded a negative magenta dye image having maximum absorption of at least 540 m and a positive yellow image with maximum at 430 mu.
The couplers of our invention are used in photographic emulsions of the developing out type.
The emulsions 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. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and Sodium chloropalladite, Which are used for sensitiz- 14 ing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, and as antiioggants 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 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), polyamines, 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(5-aminoethyl) sulfide and its watersoluble salts (Lowe and Jones U.S. Patent 2,521,926).
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; Hesseltiue U.S. Patent 2,734,900; VanLare U.S. Patent 2,739,149; and Kodak Limited British 450,958.
The emulsions can also be stabilized with the mercury compounds of Allen, Byers, and Murray U.S. Patent 2,728,663; Carroll and Murray U.S. Patent 2,728,664, and Leubner and Murray U.S. Patent 2,728,665; the triazoles of Heimbach and Kelly U.S. Patent 2,444,608; the azaindenes of Heimbach and Kelly U.S. Patents 2,444,605 and 2,444,606; Heimbach U.S. Patents 2,444,- 607 and 2,450,397; Heimbach and Clark U.S. Patent 2,444,609; Allen and Reynolds U.S. Patents 2,713,541 and 2,743,181; Carroll and Beach U.S. Patent 2,716,062; Allen and Beilfuss U.S. Patent 2,735,769; Reynolds and Sagal U.S. Patent 2,756,147; Allen and Sagura U.S. Patent 2,772,164, and those disclosed by Birr in the Z. wiss. Phot. 47, 2(1952); the quaternary b-enzothiazolium compounds of Brooker and Stand U.S. Patent 2,131,038; and the zinc and cadmium salts of Jones U.S. Patent 2,839,405.
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.
The emulsions may contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5-pentane diol as described in U.S. application Serial No. 588,951 of Milton and Murray; an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in U.S. application Serial No. 662,564 of Milton; bis-(ethoxy diethylene glycol) succinate as described in Gray U.S. Patent 2,940,854 or a polymeric hydrosol as results from the emulsion polymerization of a mixture of an amide of an acid of the acrylic acid series, an acrylic acid ester and a styrene-type compound as described in Long U.S. Patent 2,852,386. The plasticizer may be added to the emulsion before or after the addition of a sensitizing dye, if used. Y
The emulsion may be hardened with any suitable hardener for gelatin such as formaldehyde; a halogensubstituted aliphatic acid such as mucobromic acid as described in U.S. Patent 2,080,019 of White; a compound having a plurality of acid anhydride groups such as 7,8- diphenylbicyclo(2,2,2)-7-octene 2,3,5,6 tetracarboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-
disulfonyl chloride as described in U.S. Patents 2,725,- 294 and 2,725,295 of Allen and Carroll; a cyclic 1,2- diketone such as cyclopentane-1,2-dione as described in U.S. Patent 2,725,305 of Allen and Byers; a bisestcr of methane-sulfonic acid such as 1,2-di-(methanesulfonoxy)- ethane as described in U.S. Patent 2,726,162 of Allen and Laakso; 1,3-dihydroxymethylbenzimidazole-2-one as described in U.S. Patent 2,732,316 of July, Knott and Pollak; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms such as B-methyl glutaraldehyde bissodium bisulfite as described in U.S. application Serial No. 556,031 of Allen and Burness; a bis-aziridine carboxamide such as trirnethylene bis(1-aziridine carboxamide) as described in U.S. application Serial No. 599,- 891 of Allen and Webster; or 2,3-dihydroxy dioxane as described in Jefireys U.S. Patent 2,870,013.
The emulsions may have been supplied with a coating aid such as saponin; a lauryl or oleyl monoether of polyethylene glycol as described in U.S. Patent 2,831,766 of Knox and Davis; a salt of a sulfated and alkylated polyethylene glycol ether as described in U.S. Patent 2,719,- 087 of Knox and Davis; an acylated alkyl taurine such as the sodium salt of N-oleoyl-N-methyl taurine as described in U.S. Patent 2,739,891 of Knox, Twardokus, and Davis; the reaction product of a dianhydride of tetracarboxybutane with an alcohol or an aliphatic amine containing from 8 to 18 carbon atoms which is treated with a base, for example, the sodium salt of the monoester of tetracarboxybutane as described in Knox, Stenberg, and Wilson U.S. Patent 2,843,487; a water-soluble maleopimarate or a mixture of a Water-soluble maleopimarate and a substituted glutamate salt as described in U.S. Patent 2,823,123 of Knox and Fowler; an alkali metal salt of a substituted amino acid such as disodium N- (carbo-p-tert.octylphenoxypentaethoxy) glutamate as described in U.S. application Serial No. 600,679 of Knox and Wilson; or a sulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate or N-lauryl disodium sulfosuccinamate as described in U.S. application Serial No. 691,125 of Knox and Stenbcrg.
The couplers which we have described may be used in various kinds of photographic emulsions. Various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide. The couplers can be used in emulsions of the mixed-packet type, such as described in Godowsky U.S. Patent 2,696,794 or emulsions of the mixed-grain type, such as described in Carroll and Hanson U.S. Patent 2,592,243. These agents can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly inside the silver halide crystal, such as those described in Davey and Knott U.S. Patent 2,592,250.
In the preparation of the silver halide dispersions employed for preparing silver halide emulsions there may be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as 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 19-26% 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 025-15 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 cyanoacetate 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 Illingsworth, Dann, and Gates U.S. Patent 2,852,382.
If desired, compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide in its preparation.
Photographic emulsions containing our couplers may be coated on transparent supports such as glass, cellulose esters, or on a non-transparent reflecting material such as paper or opaque cellulose ester.
Our yellow-colored magenta-forming 3-anilino-4-ary1- azo-5-pyrazolone couplers described hereinabove are superior to the colored magenta-forming couplers known and used before to correct the undesired blue absorption of the magenta dye formed upon color development. They are characterized by being completely reactive with oxidized primary aromatic amino developing agents when they are used in emulsion dispersions having a coupler to coupler incorporating solvent ratio of 1: 4 and give complete compensation for unwanted blue absorption of the magenta dye when incorporated in the proper amount. This valuable characteristic is very unexpected since the corresponding 3-benzamido-4-arylazo-S-pyrazolone couplers which are very similar chemically to our couplers are completely unreactive at the desired coupler-to-coupler incorporating solvent ratio of 1:% and give no color correction. Furthermore, our couplers are characterized by having an extinction coefficient of 2.8 10 in butyl acetate which is surprisingly higher than the extinction coeificient of 1.5 X 10 in butyl acetate for the corresponding 3-benzamido-4-arylazo-5- pyrazolone couplers referred to above. These valuable characteristics of our couplers make it possible to get complete color correction in emulsions containing them with smaller amounts of coupler than is possible with couplers used before. Our couplers can be coated in thinner layers which makes it possible to produce images with lower minimum densities and thus produce pictures with whiter highlights. Thinner emulsion layers are often desirably employed for producing images with improved definition and resolution.
This invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spiirt and scope of the invention as described hereinabove and as defined in the appended claims.
We claim:
1. A photographic silver halide emulsion containing a yellow-colored magenta-forming coupler compound selected from those having the formula:
it i" RN l I re 0 N wherein R is a member selected from the group consisting of a phenyl radical and halogen substituted phenyl radicals; R is a member selected from the group consisting of hydrogen atoms and alkyl radicals having l to 4 carbon atoms; X, Y, and Z are selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 20 carbon atoms and where at least one of the substituents X, Y, and Z is said alkyl radical; and R" is selected from the group consisting of alkyl radicals having 1 to carbon atoms and alkoxy radicals having 1 to 10 carbon atoms, and an uncolored magenta-forming pyrazolone coupler which forms a dye of the same hue as formed by the yellow-colored magenta-forming coupler upon coupling with an oxidized primary aromatic amino developing agent.
2. A photographic silver halide emulsion containing (1) a yellow-colored magenta-forming coupler compound selected from those having the formula:
wherein R is a member selected from the group consisting of a phenyl radical and halogen substituted phenyl radicals; R is a member selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 4 carbon atoms; X, Y, and Z are selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 20 carbon atoms and where at least one of the substituents X, Y, and Z is said alkyl radical; R" is selected from the group consisting of alkyl radicals having from 1 to 10 carbon atoms and alkoxy radicals having 1 to 10 carbon atoms, and (2) an uncolored magentaforming coupler which both form the same magenta dye, said uncolored coupler having the formula:
gl l wherein R, R, X, Y, and Z are as defined above and where at least one of the substituents X, Y, and Z is said alkyl radical.
3. A photographic silver halide emulsion containing a yellow-colored magenta-forming coupler selected from the group consisting of compounds of the formula:
ll N wherein R is a member selected from the group consisting of phenyl radicals and halogen substituted phenyl radicals; R is a member selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 4 carbon atoms; X, Y and Z are selected from the group consisting of hydrogen atoms and alkyl radicals having 1 to 20 carbon atoms and where at least one of the substituents X, Y, and Z is said alkyl radical; R" is selected from the group consisting of alkyl radicals 18 having from 1 to 10 carbon atoms and alkoxy radicals having from 1 to 10 carbon atoms.
4. A photographic silver halide emulsion containing the yellow-colored magenta-forming coupler compound 1-(2',4',6,trichloropl1enyl) 3 {4"-[a-(2"',4"-di-tertiaryamylphenoxy)-butyrarnido]anilino} 4 (4"-methoxyphenyl) azo-S-pyr azolone.
5. A photographic silver halide emulsion containing the yellow-coloredmagenta-forming coupler compound 1-(2',4',6',trich1orophenyl) 3 {4"-[a-(2"',4"'-di-tertiaryamylphenoxy)-butyramid0]ani1ino} 4 (2""-ethoxyphenyl)azo-5-pyrazolone.
6. A photographic silver halide emulsion containing the yellow-colored magenta-forming coupler compound 1-(2,4',6,trichlorophenyl) 3 {4"-[a-(2",4"-di-tertiaryamylphenoxy)-butyramido]a11ilino} 4 (4""-dodecoxyphenyl) azo-S-pyrazolone.
7. A photographic silver halide emulsion containing the yellow-colored magenta-forming coupler compound l-phenyl 3 {4-[a-(2"',4-di-tertiaryamylphenoxy)- butyramidojanilino} 4 (4"-methoxyphenyl(azo-5-py razolone.
8. A photographic silver halide emulsion containing the yellow-colored magenta-forming coupler compound 1-(2',4',6',trichlorophenyl) 3 {4"[oc-(2"',4"'di-teltlaryarylamylphenoxy)-butyramido] anilino} 4 (4""-secondaryamylphenyl) azo-S -pyrazolone.
9. A photographic silver halide emulsion containing the yellow-colored magentaforming coupler compound 1-(2',4',6,trichlorophenyl) 3 {4-[a-(2,4"-di-tertiaryamylphenoxy)-butyramido]-ani1ino} 4 (4"-methoxyphenyl) azo-S-pyrazolone and the uncolored magentaforming coupler compound l-(2',4,6'-trichlorophenyl)-3- {4" [oc-(2"',4"' di-tertiaryamylphenoxy)butyramidolanilino}-5-pyrazolone.
10. A photographic silver halide emulsion containing the yellow-colored magenta-forming coupler compound l-(2,4',6,trich1orophenyl) 3 {4-[ot-(2,4"'-di-tel1i aryarnylphenoxy)-butyramido] aniline} 4 (2"-ethoxyphenyl)azo-5-pyrazolone, and the uncolored magentaforming coupler compound 1-(2,4,6-trich1orophenyl)- 3-{4" [u-(2,4'-di-tertiaryamylphenoxy) butyramidoJ- anilino}-5-pyrazolone.
11. A photographic silver halide emulsion containing the yellow-colored magenta-forming coupler compound 1-(2,4,6',trichlorophenyl) 3 {4"-[a-(2",4-di-tertiaryamylphenoxy)-butyramido]aniline} 4 (4""-dodec oxyphenyl) azo-S-pyrazolone and the uncolored magentaforming coupler compound 1-(2,4',6-trichlorophenyl)- 3{4"-[0a-(2"',4"' di tertiaryamylphenoxy)butyramido]anilino}-5-pyrazolone.
12. A photographic silver halide emulsion containing the yellow-colored magenta-forming coupler compound l-phenyl 3 {4"-[u-(2',4'-di-tertiaryamylphenoxy)- butyramido'janilino} 4 (4"-methoxyphenyl)azo-S- pyrazolone and the uncolored magenta-forming coupler compound 1-phenyl-3-{4"-[a-(2",4"-di-tcrtiaryarylamylphenoxy) butyramido] anilino} -5 -pyrazolone.
13. A photographic silver halide emulsion containing the yellow-colored magenta-forming coupler compound 1-(2',4',6,trichlorophenyl) 3 {4"-[a-(2,4"-di-tertiaryarylamylphenoxy)butyramido] aniline} 4 (4"-secondaryamylphenyl)azo-S-pyrazolone, and the uncolored magenta-forming coupler compound 1-(2',4',6'-trichlor0- phenyl) 3 {4" [a-(2',4' di-tertiaryamylphenoxy)- butyramido] anilino} -5-pyrazolone.
References Cited in the file of this patent UNITED STATES PATENTS 2,584,349 Heimbach Feb. 5, 1952 2,681,338 Harrison et al June 15, 1954 2,725,291 Graham Nov. 29, 1955 2,766,231 Bolliger Oct. 9, 1956

Claims (1)

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A YELLOW-COLORED MAGENTA-FORMING COUPLER COMPOUND SELECTED FROM THOSE HAVING THE FORMULA:
US765315A 1958-10-06 1958-10-06 Yellow-colored magenta-forming couplers Expired - Lifetime US2983608A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US765315A US2983608A (en) 1958-10-06 1958-10-06 Yellow-colored magenta-forming couplers
FR806824A FR1238590A (en) 1958-10-06 1959-10-06 New chromogenic coupler and its applications, particularly in photography
GB33779/59A GB937621A (en) 1958-10-06 1959-10-06 Improvements in colour photography and in colour-forming phenylazo-pyrazolones therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US765315A US2983608A (en) 1958-10-06 1958-10-06 Yellow-colored magenta-forming couplers

Publications (1)

Publication Number Publication Date
US2983608A true US2983608A (en) 1961-05-09

Family

ID=25073218

Family Applications (1)

Application Number Title Priority Date Filing Date
US765315A Expired - Lifetime US2983608A (en) 1958-10-06 1958-10-06 Yellow-colored magenta-forming couplers

Country Status (3)

Country Link
US (1) US2983608A (en)
FR (1) FR1238590A (en)
GB (1) GB937621A (en)

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3127269A (en) * 1961-09-11 1964-03-31 Colour photography
US3227554A (en) * 1959-04-06 1966-01-04 Eastman Kodak Co Photographic elements and processes utilizing mercaptan-forming couplers
US3311476A (en) * 1962-12-26 1967-03-28 Eastman Kodak Co Two-equivalent couplers for color photography
US3312715A (en) * 1963-06-17 1967-04-04 Ilford Ltd Colour couplers and their production and use in colour photography
US3328419A (en) * 1963-06-17 1967-06-27 Ilford Ltd Colour couplers and their production and use in colour photography
US3369899A (en) * 1963-07-09 1968-02-20 Gevaert Photo Prod Nv Photographic materials containing aroylacetanilide type color couplers
US3393040A (en) * 1963-07-09 1968-07-16 Gevaert Photo Prod Nv Silver halide photographic elements containing sulfonic acid substituted aroylacetarylide couplers
US3393041A (en) * 1963-07-09 1968-07-16 Gevaert Photo Prod Nv Multilayer silver halide elements containing thiazole color couplers for yellow
DE2112729A1 (en) * 1970-03-20 1971-09-30 Eastman Kodak Co Color photographic recording material
US3808007A (en) * 1970-08-29 1974-04-30 Agfa Gevaert Ag Diffusion-resistant purple color couplers for the preparation of photographic color pictures
DE2415132A1 (en) * 1973-03-31 1974-10-10 Konishiroku Photo Ind COLOR PHOTOGRAPHIC PURPLE RED COUPLER AND COLOR PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIAL CONTAINING IT
US4013635A (en) * 1975-02-26 1977-03-22 Eastman Kodak Company Cyan azo dye-providing compounds
US4228070A (en) * 1979-02-28 1980-10-14 Eastman Kodak Company Purification of photographic image-forming sulfonamido compounds employing immiscible solvents
US4272434A (en) * 1976-09-10 1981-06-09 Eastman Kodak Company Nondiffusible compounds having a releasable azo dye moiety
US4277559A (en) * 1976-02-23 1981-07-07 Agfa-Gevaert N.V. Novel magenta-forming color couplers and their use in photography
US4277398A (en) * 1976-11-15 1981-07-07 Ciba-Geigy Ag Magenta-masked color azopyrazolinone couplers
US4278598A (en) * 1974-12-20 1981-07-14 Eastman Kodak Company Positive-working immobile intramolecular nucleophilic displacement compounds and photographic elements containing same
US4281143A (en) * 1979-09-04 1981-07-28 Eastman Kodak Company Process for preparing 1-aryl-3-amino-5-pyrazolones
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
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
EP0213490A3 (en) * 1985-08-24 1988-11-23 Agfa-Gevaert Ag Colour-photographic recording material
US5219719A (en) * 1990-05-11 1993-06-15 Konica Corporation Silver halide color photographic light-sensitive material with colored magenta coupler
US5238797A (en) * 1991-08-26 1993-08-24 Konica Corporation Silver halide color photographic light-sensitive material containing a 1-pentahalogenophenyl-substituted 5-pyrazolone colored magenta coupler
JPH0677141B2 (en) 1986-01-20 1994-09-28 コニカ株式会社 Silver halide color photographic light-sensitive 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
EP0661591A2 (en) 1993-12-29 1995-07-05 Eastman Kodak Company Photographic elements containing loaded ultraviolet absorbing polymer latex
EP0684511A1 (en) 1994-05-20 1995-11-29 Eastman Kodak Company Low contrast film
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
EP0695968A2 (en) 1994-08-01 1996-02-07 Eastman Kodak Company Viscosity reduction in a photographic melt
EP0711804A2 (en) 1994-11-14 1996-05-15 Ciba-Geigy Ag Latent light stabilizers
EP0717313A1 (en) 1994-11-30 1996-06-19 Eastman Kodak Company Benzotriazole based UV absorbing compounds and photographic elements containing them
EP0762198A1 (en) 1995-08-02 1997-03-12 Eastman Kodak Company Filter dyes for photographic elements
EP0773471A2 (en) 1995-11-13 1997-05-14 Eastman Kodak Company Photographic element comprising a red sensitive silver halide emulsion layer
EP0778493A1 (en) 1995-11-30 1997-06-11 Eastman Kodak Company Aggregated dyes for radiation-sensitive elements
EP0786691A1 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
EP0786690A2 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
EP0786692A1 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
WO2013032827A1 (en) 2011-08-31 2013-03-07 Eastman Kodak Company Motion picture films to provide archival images

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2584349A (en) * 1944-11-10 1952-02-05 Gen Aniline & Film Corp Color forming development with an aromatic primary amino developer and alpha-[4-sulfophenylazo]-aceto-acet-2-4-dichloroanilide
US2681338A (en) * 1950-04-24 1954-06-15 Ici Ltd Azo coloring salts
US2725291A (en) * 1952-05-01 1955-11-29 Eastman Kodak Co Azo dye couplers having two coupling nuclei
US2766231A (en) * 1953-01-28 1956-10-09 Ciba Ltd Monoazo-dyestuffs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2584349A (en) * 1944-11-10 1952-02-05 Gen Aniline & Film Corp Color forming development with an aromatic primary amino developer and alpha-[4-sulfophenylazo]-aceto-acet-2-4-dichloroanilide
US2681338A (en) * 1950-04-24 1954-06-15 Ici Ltd Azo coloring salts
US2725291A (en) * 1952-05-01 1955-11-29 Eastman Kodak Co Azo dye couplers having two coupling nuclei
US2766231A (en) * 1953-01-28 1956-10-09 Ciba Ltd Monoazo-dyestuffs

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3227554A (en) * 1959-04-06 1966-01-04 Eastman Kodak Co Photographic elements and processes utilizing mercaptan-forming couplers
US3127269A (en) * 1961-09-11 1964-03-31 Colour photography
US3311476A (en) * 1962-12-26 1967-03-28 Eastman Kodak Co Two-equivalent couplers for color photography
US3312715A (en) * 1963-06-17 1967-04-04 Ilford Ltd Colour couplers and their production and use in colour photography
US3328419A (en) * 1963-06-17 1967-06-27 Ilford Ltd Colour couplers and their production and use in colour photography
US3369899A (en) * 1963-07-09 1968-02-20 Gevaert Photo Prod Nv Photographic materials containing aroylacetanilide type color couplers
US3393040A (en) * 1963-07-09 1968-07-16 Gevaert Photo Prod Nv Silver halide photographic elements containing sulfonic acid substituted aroylacetarylide couplers
US3393041A (en) * 1963-07-09 1968-07-16 Gevaert Photo Prod Nv Multilayer silver halide elements containing thiazole color couplers for yellow
DE2112729A1 (en) * 1970-03-20 1971-09-30 Eastman Kodak Co Color photographic recording material
US3808007A (en) * 1970-08-29 1974-04-30 Agfa Gevaert Ag Diffusion-resistant purple color couplers for the preparation of photographic color pictures
DE2415132A1 (en) * 1973-03-31 1974-10-10 Konishiroku Photo Ind COLOR PHOTOGRAPHIC PURPLE RED COUPLER AND COLOR PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIAL CONTAINING IT
US4278598A (en) * 1974-12-20 1981-07-14 Eastman Kodak Company Positive-working immobile intramolecular nucleophilic displacement compounds and photographic elements containing same
US4013635A (en) * 1975-02-26 1977-03-22 Eastman Kodak Company Cyan azo dye-providing compounds
US4277559A (en) * 1976-02-23 1981-07-07 Agfa-Gevaert N.V. Novel magenta-forming color couplers and their use in photography
US4272434A (en) * 1976-09-10 1981-06-09 Eastman Kodak Company Nondiffusible compounds having a releasable azo dye moiety
US4277398A (en) * 1976-11-15 1981-07-07 Ciba-Geigy Ag Magenta-masked color azopyrazolinone couplers
US4228070A (en) * 1979-02-28 1980-10-14 Eastman Kodak Company Purification of photographic image-forming sulfonamido compounds employing immiscible solvents
US4281143A (en) * 1979-09-04 1981-07-28 Eastman Kodak Company Process for preparing 1-aryl-3-amino-5-pyrazolones
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
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
EP0213490A3 (en) * 1985-08-24 1988-11-23 Agfa-Gevaert Ag Colour-photographic recording material
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
JPH0677141B2 (en) 1986-01-20 1994-09-28 コニカ株式会社 Silver halide color photographic light-sensitive 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
US5219719A (en) * 1990-05-11 1993-06-15 Konica Corporation Silver halide color photographic light-sensitive material with colored magenta coupler
US5238797A (en) * 1991-08-26 1993-08-24 Konica Corporation Silver halide color photographic light-sensitive material containing a 1-pentahalogenophenyl-substituted 5-pyrazolone colored magenta coupler
EP0661591A2 (en) 1993-12-29 1995-07-05 Eastman Kodak Company Photographic elements containing loaded ultraviolet absorbing polymer latex
EP0684511A1 (en) 1994-05-20 1995-11-29 Eastman Kodak Company Low contrast film
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
EP0695968A2 (en) 1994-08-01 1996-02-07 Eastman Kodak Company Viscosity reduction in a photographic melt
EP0711804A2 (en) 1994-11-14 1996-05-15 Ciba-Geigy Ag Latent light stabilizers
EP0717313A1 (en) 1994-11-30 1996-06-19 Eastman Kodak Company Benzotriazole based UV absorbing compounds and photographic elements containing them
EP0762198A1 (en) 1995-08-02 1997-03-12 Eastman Kodak Company Filter dyes for photographic elements
EP0773471A2 (en) 1995-11-13 1997-05-14 Eastman Kodak Company Photographic element comprising a red sensitive silver halide emulsion layer
EP0778493A1 (en) 1995-11-30 1997-06-11 Eastman Kodak Company Aggregated dyes for radiation-sensitive elements
EP0786691A1 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
EP0786690A2 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
EP0786692A1 (en) 1996-01-26 1997-07-30 Eastman Kodak Company Silver halide light sensitive emulsion layer having enhanced photographic sensitivity
WO2013032827A1 (en) 2011-08-31 2013-03-07 Eastman Kodak Company Motion picture films to provide archival images

Also Published As

Publication number Publication date
GB937621A (en) 1963-09-25
FR1238590A (en) 1960-08-12

Similar Documents

Publication Publication Date Title
US2983608A (en) Yellow-colored magenta-forming couplers
US3408194A (en) Silver halide emulsion layers containing yellow dye forming couplers
US3265506A (en) Yellow forming couplers
US3034892A (en) Magenta-colored cyan-forming couplers
US3617291A (en) Two-equivalent couplers for photography
US3062653A (en) Photographic emulsion containing pyrazolone magenta-forming couplers
US4427767A (en) Color photographic sensitive materials
US4525450A (en) Silver halide color photographic light sensitive material containing a coupler containing at least one of a sulfamoylphenylenesulfonyl, sulfamoylaminophenylenesulfonyl, or sulfoamidophenylenesulfonyl group
US3311476A (en) Two-equivalent couplers for color photography
US3749735A (en) Certificate of correction
US4513082A (en) Silver halide color photographic light-sensitive materials
US3447928A (en) Silver halide emulsion containing twoequivalent yellow dye-forming coupler
US2808329A (en) Photographic color correction using colored and uncolored couplers
US4264721A (en) Color photographic materials
US3384657A (en) Acetoacetamide couplers in which the non-oxo carbon atom of the aceto group is a tertiary carbon atom
US4404274A (en) Photographic light sensitive element containing yellow color coupler and method for forming yellow photographic images
US4503141A (en) Silver halide color photographic light-sensitive materials containing couplers with a hydroxyl substituted aromatic heterocyclic sulfonyl group in the ballast group
JPH0316011B2 (en)
US4157919A (en) Silver halide emulsions containing yellow-dye-forming couplers
JPS60218645A (en) Silver halide photographic material
US4269936A (en) Process of forming yellow photographic images
US4345024A (en) Photographic development inhibitor releasing compound
US3006759A (en) Two-equivalent magenta-forming couplers for color photography
USRE27848E (en) We length in millimicrons
US4336327A (en) Silver halide emulsion containing yellow coupler