US3227551A - Photographic color reproduction process and element - Google Patents

Photographic color reproduction process and element Download PDF

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Publication number
US3227551A
US3227551A US244774A US24477462A US3227551A US 3227551 A US3227551 A US 3227551A US 244774 A US244774 A US 244774A US 24477462 A US24477462 A US 24477462A US 3227551 A US3227551 A US 3227551A
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United States
Prior art keywords
coupler
color
couplers
sensitive
layer
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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
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US244774A
Inventor
Charles R Barr
Williams John
Whitmore Keith
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
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Eastman Kodak Co
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Publication date
Priority to BE619300D priority Critical patent/BE619300A/xx
Priority to BE589419D priority patent/BE589419A/xx
Priority to BE619301D priority patent/BE619301A/xx
Priority to BE591444D priority patent/BE591444A/xx
Priority claimed from US804219A external-priority patent/US3148062A/en
Priority to DE19601422836D priority patent/DE1422836B1/en
Priority to FR823429A priority patent/FR1257887A/en
Priority to GB12109/60A priority patent/GB953454A/en
Priority to DE19601422839 priority patent/DE1422839A1/en
Priority to FR828864A priority patent/FR78161E/en
Priority to DE19621422860 priority patent/DE1422860A1/en
Priority to DEE22970A priority patent/DE1199129B/en
Priority to FR901601A priority patent/FR1339555A/en
Priority to FR901602A priority patent/FR1335025A/en
Priority to GB24885/62A priority patent/GB1014725A/en
Priority to US244774A priority patent/US3227551A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US270709A priority patent/US3227554A/en
Priority to US507975A priority patent/US3701783A/en
Publication of US3227551A publication Critical patent/US3227551A/en
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    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/63—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
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    • 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
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    • 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
    • C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
    • C07D231/32—Oxygen atoms
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    • 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
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    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
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    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
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    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
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    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/06—Hydroxy derivatives of triarylmethanes in which at least one OH group is bound to an aryl nucleus and their ethers or esters
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    • C09B31/02—Disazo dyes
    • C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
    • C09B31/061—Disazo dyes from a coupling component "C" containing a directive hydroxyl group containing acid groups, e.g. -CO2H, -SO3H, -PO3H2, -OSO3H, -OPO2H2; Salts thereof
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    • C09B31/02—Disazo dyes
    • C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
    • C09B31/075—Disazo dyes from a coupling component "C" containing a directive hydroxyl group ortho-Hydroxy carboxylic acid amides
    • C09B31/078—Disazo dyes from a coupling component "C" containing a directive hydroxyl group ortho-Hydroxy carboxylic acid amides containing acid groups, e.g. —COOH, —SO3H, —PO3H2, —OSO3H, —OPO2H2; Salts thereof
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    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • 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
    • G—PHYSICS
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    • 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
    • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
    • G03C7/30552—Mercapto
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
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    • 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
    • G—PHYSICS
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    • 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
    • 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
    • G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/156—Precursor compound
    • Y10S430/158—Development inhibitor releaser, DIR

Definitions

  • Sheets-Sheet 1 PROTECTIVE LAYER AgX BLUE SENSITIVE EMULSION INH/BI TIN G COUPL ER FOGGED AgX+YELLOW-FORMlIV6 COUPLER BARR/ER LAYER AgX RED-SENSITIVE EMULSION l6 VIIIIJJIA. INHIBIT/N6 COUPLER l5 mwwmw F06650 Ag)! CYAN- FORM/N6 COUPLER /4 VIII. m BARR/ER LAYER /3 mm? Agx 6R.
  • EMULSION 53 NUCLEATED METAL SALT+ CYAIV-FORM/NG COUPLER 62 STR/PP/NG LAYER 5/ MORDANTED RECEPTION LAYER 6 SUPPORT CHARLES R BARR JOHN WILLIAMS KEITH E WH/ TMORE INVENTORS BY A ATTORNEYS United States Patent 3,227,551 PHOTOGRAPHIC COLOR REPRODUCTION PROCESS AND ELEMENT Charles R. Barr, John Williams, and Keith Whitmore,
  • This invention relates to color photography, and more particularly, to photographic direct positive color diffusion transfer processes and photographic elements suitable for use in such processes.
  • Direct positive photographic color processes are well known in the art, and generally comprise a number of steps.
  • a typical color process comprises such steps as a black-and-white development to form a negative image, a reversal exposure, development with an aromatic primary amino color developing agent to form insoluble image dyes in the areas of development, and a bleach step to remove developed silver.
  • Color proceses are also known whereby color images are transferred to receiving elements, and which have the advantage of producing color images free of residual color couplers and other products of development.
  • many of such processes of the latter type involve several complex steps, require several processing baths with large volumes of processing solutions, and produce poor quality color images due to lateral diffusion of dye-forming components.
  • the present invention concerns light-sensitive photographic elements having coated thereon at least two Color- Forming Units as described herein, and which elements can be processed in the presence of alkaline color developing solutions containing aromatic primary amino color developing agents to prepare direct positive color images.
  • the Color-Forming Units of the invention comprise:
  • Component A A hydrophilic colloid-silver halide emulsion capable of recording latent images on exposure to light;
  • Component B A photographic color coupler capable of forming a diffusible mercaptan development inhibitor on development with an alkaline color developing solution containing an aromatic primary amino color developing agent, such development inhibitor-releasing couplers being referred to herein as DIR couplers (this component can be either in the Color-Forming Unit or the color developing solution);
  • Component D.--A nondifiusible photographic color coupler capable of forming a diftusible acid dye on development with an alkaline color developing solution containing an aromatic primary amino color developing agent, and which dittusible dye-releasing coupler is referred to herein as a DDR coupler,
  • a latent image (negative image) pattern of developable silver halide is formed in the light-sensitive emulsion (Component A).
  • this exposed emulsion is developed in an alkaline color developing solution containing an aromatic primary amino color developing agent in the presence of a DIR coupler (Component B)
  • the DIR coupler reacts with color development oxidation product to form a ditt'usible mercaptan development inhibitor.
  • the resulting dilfusible developement inhibitor difiuses imagewise to the spontaneously developable emulsion (Component C) inhibiting development in regions corresponding to the latent image pattern (negative image area) formed in the light-sensitive emulsion.
  • a DDR coupler (Component D) is contiguous to the developable metal salt of the spontaneously developable emulsion.
  • the developable metal salt of the spontaneously developable emulsion in regions not inhibited against development by the diflusible development inhibitor (positive image area) develops and a ditfusible acid dye is formed in such regions when the DDR coupler reacts with color development oxidation product.
  • the resulting acid dye diffuses imagewise in register to a juxtaposed reception layer containing a mordant for acid dyes to produce a positive color reproduction.
  • the Color-Forming Units are prepared so that the light-sensitive emulsion develops and a development inhibitor is released a finite time prior to the development of the spontaneously developable emulsion and the subsequent release of the ditfusible dye.
  • Such can be accomplished by physically disposing the light-sensitive emulsion (Component A) and the contiguous DIR coupler (Component B) further from the support than the spontaneously developable emulsion, by utilizing a silver halide emulsion having a shorter development induction period for the light-sensitive emulsion than the developable metal salt in the spontaneously developable emulsion, and/or by utilizing DIR couplers that react at a faster rate than the DDR couplers.
  • the DDR couplers are integral components of the present elements while the DIR couplers can be either integral components or used in the alkaline color developing solution.
  • the DIR coupler can either be incorporated in, or in a layer contiguous to, the light-sensitive emulsion, and the DDR coupler can be either incorporated in, or in a layer contiguous to, the spontaneously developable emulsion.
  • lhotographic elements suitable for preparing correct full-color positive renditions can be prepared by utilizing three of the present Color-Forming Units wherein the light-sensitive emulsions are sensitive to red, green and 3 blue light respectively, and the DDR couplers are couplers capable of forming dir'fusible acid dyes complementary to the color of the spectral sensitivity of the respective Color-Forming Units.
  • false sensitization can also be utilized in preparing the present photographic elements.
  • the DDR or difiusible dye-releasing couplers used in the photographic elements of the invention are initially nondiffusing in the layers of the element but form dyes diffusible in the layers of the element on reaction with oxidation product of aromatic primary amino silver halide photographic color developing agents.
  • Such DDR couplers include those having the formulas:
  • DYE is a dye radical containing an acidic solubilizing radical
  • COUP is a photographic color coupler radical such as a S-pyrazolone coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, the coupler radical being substituted in the coupling position with the connecting or linkage radical;
  • BALL is a photographically inert organic radical of such molecular size and configuration as to render the coupler nondiffusing in the element in the alkaline color developing solution;
  • SOL is either a hydrogen atom or an acidic solubilizing group when the color developing agent contains an acidic solubilizing radical, SOL always being an acidic solubilizing radical when the color developing agent is free of an acidic solubilizing group;
  • n is an integer of l or 2 when LINK is an alkylidene radical, and n is always 1 when LINK is one of the other aforementioned connecting radicals, namely, azo, azoxy, mercuri, oxy, thio, or dithio.
  • the acidic solubilizing radicals attached to the diffusible dye-releasing (DDR) couplers described above can be solubilizing radicals which when attached to the coupler or developer moieties of the dies, render the dyes diffusible in the element in alkaline processing solutions.
  • Typical of such radicals are carboxylic, sulfonic, ionizable sulfonamido, and hydroxy-substituted groups that lend to dyes negative charges.
  • Typical dye radical substituents (DYE) of the DDR couplers include azo, azomethine, indoaniline, indophenol, anthraquinone and related dye radicals Well known in the art that exhibit selective absorption in the visible spectrum.
  • the dye radicals contain acidic solubilizing moieties.
  • DDR couplers having the formula DYE-LINK- (COUP-BALL) as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a dilfusible preformed acid dye (DYE) is released which diffuses imagewise to a reception layer.
  • DYE dilfusible preformed acid dye
  • An acidic solubilizing group on the preformed dye lends diffusibility and mordantability to the dye molecule.
  • the coupling portion of the DDR coupler (COUP) couples with color developing agent oxidation product to form a dye that is nonditfusible in the element because of the attached ballasting group (BALL) in a noncoupling position.
  • the color of the diffusible dye is determined by the color of the preformed dye moiety (DYE), the color of the reaction product of color developer oxidation product and the coupler moiety (COUP) being unimportant to the color of the ditfusible image.
  • DDR couplers having the formula BALL-LINK- (COUP-SOL) as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a ditfusible dye is formed with the color developing agent oxidation product and the coupling portion (COUP) of the DDR coupler which diffuses imagewise to a reception layer. Diffusibility is imparted to the dye by an acidic solubilizing group attached to a noncoupling position of the coupling portion (COUP) of the DDR coupler or to the color developing agent. The ballast portion of the DDR coupler remains im mobile. In this type of DDR coupler, the color of the diifusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COUP).
  • the coupler radical (COUP) in the DDR couplers is a S-pyrazolone radical
  • the coupler radical (COUP) in the DDR couplers is a cyan-forming phenolic coupler radical
  • we prefer to have substituted in the ortho or 2-position of the phenolic moiety a fully substituted amido group e.g.,
  • BALL-LINK-(COUP-SOL) is an azo radical
  • the ballasting radical (BALL) be a phenyl radical containing either a hydroxy group or an amino group (NH substituted in the ortho or 2-position of the phenyl moiety.
  • the DIR or development inhibitor-releasing couplers used in the photographic elements of the invention release or form development inhibitors that are ditfusi'ole in the layers of the Color-Forming Unit on reaction with oxidation product of aromatic primary amino silver halide photographic color developing agents.
  • ballasting groups are used to make the coupler nondifiusible in the layers of the Color-Forming Unit in alkaline color developing solutions. Such ballasted DIR couplers are preferred.
  • the DIR couplers are utilized in the color developing solution, the DIR couplers are free of ballasting groups and are ditfusible in the layers of the element in alkaline color developing solutions.
  • DIR couplers of the invention include those having the formulas:
  • BALL is a ballast group as described above for the DDR couplers
  • LINK is a connecting or linkage radical as described above for the DDR couplers
  • m is an integer of 0 or 1;
  • n is an integer of 1 or 2 as described above for the DDR couplers
  • COUP is a photographic color coupler radical as described above for the DDR couplers
  • MERC is a ditfusible radical containing a mercapto radical (SH).
  • RAD is a photographically inert, ditfusible radical that forms a mercaptan with the monothio connecting or linkage radical (S).
  • a wide variety of photographically inert radicals that are diflfusible in the layers of the Color-Forming Unit and form mercaptans with the monothio connecting or linkage radical when the connecting radical is split on development can be used for the RAD substituent of the DIR couplers.
  • Typical of such radicals are aryl, alkaryl and carbon-containing heterocyclic radicals.
  • the aryl moiety of such radicals is preferably phenyl, and includes such substituents as nitro, lower alkyl, lower alkylamido, lower alkoxy, lower alkylsulfoamido, lower alkylcarbamyl, carbon-containing heterocyclic radicals and the like.
  • the carbon-containing heterocyclic radicals which can be attached directly to the monothio linkage radical or as a substituent on the described aryl moieties, generally contain at least one hetero nitrogen, oxygen or sulfur atom, and preferably, 1 to 4 hetero nitrogen atoms.
  • the hetero nitrogen atoms in the heterocyclic radicals have no hydrogen atom attached thereto as the RAD radical is photographically inert.
  • Illustrative carbon-containing heterocyclic radicals include l-phenyltetrazolyls, oxazolyls, oxadiazolyls, diazolyls, thiadiazolyls, henzoxazolyls, benzothiazolyls, pyrimidyls, pyridinyls, quinolinyls and the like.
  • MERC is a preformed mercapto development inhibiting moiety.
  • a Wide variety of dilfusible radicals containing a mercapto radical (-SH) can be used for the MERC substituent of the DIR couplers.
  • the mercapto radical can be suitably attached to an aryl, alkaryl or a carboncontaining heterocyclic radical such as RAD described above except that it is not necessary that the hetero nitrogen atoms on the heterocyclic radicals be free of hydrogen atoms.
  • a ballast group (BALL) is utilized and m is l; and when the DIR couplers are used in the processing solution, such a ballast group is not utilized and m is 0.
  • the DIR couplers containing preformed development-inhibiting moieties (MERC) are ballasted and always utilized integral with the photographic element.
  • the spontaneously developable emulsions (Component C) are prepared to have longer development induction periods than the light-sensitive silver halide emulsrons.
  • DIR couplers having the formula (BALL- COU?) -LINK-MERC are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a mercaptan development inhibitor (MERC) is released that is diffusible in the Color-Forming Unit.
  • a ballasted or immobile dye is formed by reacting the coupler moiety (COUP) at the coupling position with oxidized color developing agent.
  • DIR couplers are preformed development inhibitors, they are utilized in a layer adjacent to the light-sensitive silver halide emulsion layer of the present Color-Forming Units.
  • a nonditrusible or a noumordantable dye is formed by reacting the coupler moiety (COUP) at the coupling position with oxidized color developing agent, both the DIR coupler and the color developing agent being free of acidic solubilizing groups when m is zero and the dye formed is difiusible.
  • the substituent, in, is preferably one, and such DIR couplers can be utilized either in the light-sensitive emulsion or in a layer adjacent thereto in the present Color-Forming Units.
  • ballast groups (BALL) in the DIR and DDR coupler compounds described above is not critical as long as they confer nondifiusibility to the coupler compounds.
  • hereinafter in the specific couplers disclosed include long chain alkyl radicals or several short chain alkyl radicals
  • Typical ballast groups exemplified having e.g., 8-22 carbon atoms, linked directly or indirectly to the coupler molecules, as well as aromatic radicals of the benzene and naphthalene series, etc., linked directly or indirectly to the coupler molecules by a splittable linkage, or by a removable or irremovable but otherwise nonfunctional linkage depending upon the nature of the coupler compound.
  • Useful ballast groups generally have at least 8 carbon atoms.
  • the S-pyrazolone coupler radicals couple at the carbon atom in the 4-position
  • the phenolic coupler radicals, including a-napthols couple at the carbon atom in the 4-position
  • the open-chain ketomethylene coupler radicals couple at the carbon atom forming the methylene moiety (e.g.,
  • nondiffusing used herein as applied to the couplers and coupler reaction products has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through organic colloid layers, such as gelatin, comprising the sensitive elements of the invention.
  • dii'fusible as applied to the mercaptan development inhibitors released from the DIR couplers and the dyes released from the DDR couplers in the present processes has the converse meaning and denotes materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of the nondiifusing materials from which they are derived in alkaline color developing solutions.
  • the silver halide emulsions of the present photographic elements are conventional developing-out photographic silver halide emulsions including silver chloride, silver bromide, silver bromoiodide, silver chlorobromide and silver chlorobromoiodide emulsions.
  • the dispersing agent or substrate for the silver halide in its preparation gelatin or some other commonly employed photographic hydrophilic colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound, although gelatin is preferred.
  • Such hydrophilic colloidal materials can also be used in the non-light-sensitive layers in the subject elements in accordance with usual practice. Such hydrophilic collids are well known in the art.
  • the subject photographic emulsions can contain the addenda generally utilized in such products including optical sensitizers, speed-increasing materials, antifoggants, coating aids, gelatin hardeners, plasticizers, ultraviolet, absorbers and the like.
  • each Color-Forming Unit in the photographic elements of the invention contains, in addition to a light-sensitive silver halide emulsion (Component A), an emulsion of a water-insoluble metal salt that is developable (i.e., reducible to metal) with alkaline color developing solutions containing aromatic primary amino color developing agents to a substantial density without light exposure of the element (Component C).
  • Component A a light-sensitive silver halide emulsion
  • Such metal salts are preferably such Water-insoluble lightsensitive silver salts such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, silver citrate, silver oxalate, silver phosphate, silver stearate, silver ferrocyanide, silver cyanide, silver thiocyanate and the like.
  • Other useful salts include palladium bromide, palladium cyanide and related heavy metal salts, as well as cuprous bromide and the like.
  • Such metal salts can be made spontaneously developable by incorporating in the emulsion a wide variety of wellknown physical development nuclei.
  • Typical development nuclei include colloidal noble metals such as silver and gold; colloidal metal sulfides, selcnides and tellurides such as lead sulfide, nickel sulfide, cadmium sulfide, silver sulfide, silver selenide, silver telluride, copper sulfide, zinc sulfide and mercury sulfide; metal proteinates such as silver proteinates; sodium sulfide; colloidal sulfur; and such organic sulfur compounds as thiourea, and xanthates.
  • developer solvents for the metal salts are utilized in the developing compositions when the physical development nuclei are employed to make the emulsions spontaneously developable, including ammonium and alkali metal thiosulfates, thiocyanates, sulfites and the like.
  • Another method that can be utilized to make the lightsensitive, Water-insoluble salts spontaneously developable is by prefogging the emulsion with light or with chemical reducing agents such as alkali metal borohydrides and the like in accordance with well-known photographic fogging techniques.
  • alkaline color developing solutions containing aromatic primary amino color developing agents can be utilized to process the present photographic elements.
  • Such developing solutions are utilized to develop or reduce to silver the exposed silver halide in the light-sensitive emulsions (Component A) to form a negative image, and to develop or reduce to a metal the metal salt in the spontaneously developable emulsion (Component C) to form a positive image.
  • Particularly useful developing agents are the well-known p-phenylenediamine color developing agents.
  • the color developing agent can be either incorporated in an alkaline photographic developing solution that is topically applied to the present photographic elements on processing, or the color developing agent can be incorporated in the element.
  • a typical Schiff base color developing agent can be prepared by reacting 2-arnino-5-diethylaminotoluene and o-sulfobenzaldehyde.
  • Other Schiff base developers that are useful as such, as salts or as sulfur dioxide complexes include:
  • Such incorporated developing agents can be activated by immersing the photographic element in an aqueous alkaline solution or by spreading an aqueous alkaline solution on the surface of the element.
  • Such incorporated developing agents can be positioned in any layer of the present photographic elements from which the developing agents can be readily made available for development on activation with aqueous alkaline solutions.
  • incorporated developing agents are either incorporated in the light-sensitive silver halide emulsion layers or in layers contiguous thereto.
  • Typical supports comprising the photographic elements of the invention include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, po1yethylene terephthalate film, polyethylene film, polypropylene film, and related films of resinous materials, as well as paper, glass, and others.
  • the above-described emulsion layers are coated on the photographic supports in the form of multilayer color photographic elements having at least two and preferably three Color-Forming Units sensitive to different regions of the visible spectrum.
  • the uppermost Color-Forming Unit is preferably selectively sensitive to blue light.
  • a yellow dye layer or Carey Lea silver layer for absorbing or filtering blue radiation that may be transmitted through the uppermost blue sensitive layer.
  • the physical disposition of the red, green and blue light-sensitive Color- Forrning Units within the present photographic elements can be Widely varied in accordance with usual practice.
  • Such multilayer photographic elements can also have other interlayers or sublayers for specialized purposes in accordance with usual practice.
  • each Color- Forming Unit can be a single layer.
  • the DIR coupler and the light-sensitive silver halide emulsion (Component A) can be substantially uniformly dispersed in packets in the spontaneously developable emulsion containing the DDR coupler.
  • the DDR coupler and the spontaneously developable emulsions can be substantially uniformly dispersed in packets in the lightsensitive silver halide emulsion containing the DIR coupler.
  • the spontaneously developable emulsions are more generally prepared to have longer development induction periods than the light-sensitive silver halide emulsions.
  • DIR couplers having faster reaction rates than the DDR couplers can be utilized in light-sensitive emulsion packets containing the DIR couplers.
  • the barrier layers contain a water-insoluble salt or metal capable of forming a water-insoluble salt with mercaptans, silver halides such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., being preferably used.
  • the barrier layers containing light-sensitive silver salts are prepared to be substantially less sensitive to light than the light-sensitive emulsions in the Color-Forming Units. Such barrier layers also serve to prevent oxidized color developing agent from wandering from one Color-Forming Unit to another where it could cause color contamina tion.
  • Antioxidants such as n-octadecyl hydroquinone and the like phenolic antioxidants, and nondiifusible photographic color couplers that form nondifiusible dyes on coupling with oxidized aromatic amino color developing agents can be utilized in the barrier layers to prevent wandering of such oxidized color developing agent.
  • the reception layer used to receive the difiused dye images on color development of the photoelements of the invention can be either a separate sheet pressed in contact with the photoelement or a layer integral with the photoelement.
  • the development and transfer operations can be efiected by bathing either or both the exposed photographic element and the mordanted reception sheet in the developing solution before rolling into contact with each other.
  • a viscous developing composition can be placed between the elements for spreading in a predetermined amount across and in contact with the exposed surface of the sensitive element so as to provide all of the solution required for the picture area.
  • the viscous developing composition is desirably utilized in one or more pods integral with the photoelement or the reception sheet that can be readily ruptured when development is desired, suitable viscous developer utilization techniques being disclosed in US. Patents 2,543,181; 2,559,643; 2,647,049; 2,647,056; 2,661,293; 2,698,244; 2,698,798; and 2,774,668.
  • a typical element of this type can comprise a support, a mordanted colloid layer thereon and the various emulsion layers described above coated thereover.
  • easily dissolved emulsions such as those containing polyvinyl alcohol or an alkali-soluble cellulose ether phthalate vehicles, or a wet or dry stripping layer containing such vehicles is provided between the emulsions and reception layer, the developed emulsion layers can then be readily separated from the reception layer leaving the dye image thereon.
  • the reception layer can be initially bonded to the outer emulsion surface. In this case, it is preferred to expose through the support of the sensitive element unless the reception layer itself is transparent.
  • Such photoelements can be processed in the same manner as those not containing integral reception layers.
  • the reception layers in the photoelements of the invention can contain any of the conventional mordant materials for acid dyes.
  • the reception layer can contain mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone described in the Minsk US. Patent 2,832,15 6 granted April 14, 1959.
  • mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al., US. Patent 2,484,430 granted October 11, 1949 and cetyl trimethylammonium bromide, etc.
  • Particularly effective mordanting compositions are described in copending applications of Knechel et al., US. Serial No. 211,095 filed July 19, 1962, and Bush, US.
  • the mordanting compositions described in the Knechel et al. application comprise at least one hydrophilic organic colloid containing a finely-divided, uniform dispersion of droplets or globules of a high-boiling, water-immiscible organic solvent in which is dissolved a high concentration of a cationic, nonpolyme'ric, organic dye-mordanting compound for acid dyes.
  • the mordanting compositions described in the Bush application comprise at least one hydrophilic organic colloid containing a finely-divided, uniform dispersion of particles of a salt of an organic acidic compmition containing free acid moieties and a cationic, nonpolymeric, organic dyemordanting compound for acid dyes.
  • Useful cationic or basic organic dye-mordanting compounds for acid dyes include quaternary ammonium and phosphonium, and ternary sulfonium compounds in which there is linked to the N, P, or S onium atom at least one hydrophobic ballast group such as long-chain alkyl or substituted alkyl groups.
  • the reception layer or sheet can be sumcient by itself to mordant the dye as in the case of the use of a sheet or layer of a polyarnide or related polymeric material.
  • Reception sheets for the dye images, as well as the photoelements of the invention can contain ultraviolet absorbing materials.
  • ultraviolet absorbers protect the mordanted dye images from fading and print-out due to ultraviolet light.
  • ultraviolet absorbers can serve as taking filters to reduce ultraviolet sensitivity. Typical ultraviolet absorbing materials are described in copending applications of Sawdey, U.S. Serial Nos. 144,228 filed October 10, 1961 and 183,417 filed March 29, 1962.
  • Illustrative useful ultraviolet absorbing materials disclosed by Sawdey have the formulas wherein: R is a phenyl radical including such substituents as hydrogen atoms, halogen atoms, alkyl radicals, alkoxy radicals or hydroxy radicals; and R R and R are hydrogen atoms, halogen atoms, nitro radicals, alkyl radicals, alkoxy radicals, aryl radicals -or aryloxy radicals. Other ultraviolet absorbing materials well known in the photographic art can also be utilized.
  • a keep-negative as well as a positive color transfer print can be prepared.
  • a conventional photographic color coupler of the type that forms a nondiifusible dye when reacted with oxidized color coupler is utilized with the DIR coupler.
  • DDR couplers are chosen that do not form colored nondiffusible dyes during the present process.
  • the DIR couplers are chosen so that the dyes which are formed are either diffusible or have absorptions similar to those of the respective keep-negative nondiffusible couplers.
  • the reception layer used to receive the diifused positive dye image is a separate receiving sheet not integral with the element.
  • Suitable photographic color coupl-ers that form nondifiusible dyes are of the phenolic, S-pyrazolone and open-chain ketomethylene type such as those disclosed in Spence et al., U.S. Patent 2,640,776; Weissberger et al., US. Patent 2,407,210; and Weissberger et al., US. Patent 2,474,293.
  • FIG. 1 illustrates a typical photographic element of the invention wherein the DIR or development inhibitorreleasing coupler is positioned in a layer contiguous to the light-sensitive silver halide emulsion and the spontaneously developable emulsion comprises a fogged silver halide emulsion in each Color-Forming Unit.
  • FIG. 2 illustrates a typical photographic element of the invention wherein the DIR coupler is positioned in the light-sensitive silver halide emulsion and the spontane ously developable emulsion comprises a fogged silver halide emulsion in each Color-Forming Unit.
  • FIG. 3 illustrates a typical photographic element of the invention in which each Color-Forming Unit is a single layer wherein packets of silver halide and the DIR coupler are dispersed in a fogged silver halide emulsion containing the DDR or diffusible dye-releasing couplers.
  • FIG 3 includes an enlarged section of one Color- Forming Unit.
  • FIG. 4 illustrates a typical photographic element of the invention wherein the DIR coupler is positioned in the light-sensitive silver halide emulsion and the spontaneously developable emulsion comprises a nucleated metal salt in each Color-Forming Unit.
  • FIG. 5 illustrates a typical photographic element of the invention similar to that of FIG. 4 except that an integral mord-anted reception layer is present as well as a stripping layer to facilitate the removal of the Color- Forming Units after processing.
  • color-Forming Units of the invention that are sensitive to a different region of the visible spectrum.
  • On support 10 is coated fogged silver halide emulsion layer 11 containing a magenta-forming DDR coupler.
  • Over layer 11 is coated development-inhibiting layer 12 containing a DIR coupler.
  • silver halide R and R To complete the Color-Forming Unit nearest the support, silver halide R and R;
  • barrier layer 14 that contains a compound capable of forming an insoluble salt with mercaptans such as a silver halide.
  • barrier layers can contain antioxidants or nonditlusible color couplers that form insoluble dyes on reaction with oxidized color developing agent, such a-ddenda serving to minimize wandering of oxidized color developer and thu reducing color fog.
  • barrier layer 14 is coated fogged silver halide emulsion layer 15 containing a cyan-forming DDR coupler.
  • Over layer 15 is coated development inhibitor layer 16 containing a DIR coupler.
  • silver halide emulsion layer 17 that is sensitive to red light'is coated over layer 16.
  • Barrier layer 18 containing a compound capable of forming an insoluble salt with mercaptans and a filter for blue light such as a yellow coupler, a yellow dye or Carey Lea silver is coated over layer 17.
  • Over barrier layer 18 is coated fogged silver halide emulsion layer 19 containing a yellow-forming DDR coupler.
  • Over layer 19 is coated development inhibiting layer 20 containing a DIR coupler.
  • silver halide emulsion layer 21 that is sensitive to blue light is coated over layer 20.
  • a layer of a hydrophilic colloid such a protective layer 22 is coated on layer 21.
  • On photographic support are coated three Color-Forming Units of the invention that are sensitive to different regions of the visible spectrum.
  • On support 30 is coated fogged silver halide emulsion layer 31 containing a magenta-forming DDR coupler.
  • Over layer 31 is coated silver halide emulsion layer 32 that is sensitive to green light and contains a DIR coupler.
  • Over layer 32 is coated barrier layer 33 containing a compound capable of forming an insoluble salt with mercaptans.
  • Over layer 33 is coated fogged silver halide emulsion layer 34 containing a cyan-forming DDR coupler.
  • Over layer 34 is coated silver halide emulsion layer 35 that is sensitive to red light and contains a DIR coupler.
  • barrier layer 36 containing a compound capable of forming an insoluble salt with mercaptans and a yellow filter material is coated.
  • Over layer 36 is coated fogged silver halide emulsion layer 37 containing a yellow-forming DDR coupler.
  • Over layer 37 is coated silver halide emulsion layer 38 that is sensitive to blue light and contains a DIR coupler.
  • Over layer 38 is coated protective layer 39.
  • each Color-Forming Unit comprises a single layer, namely layers 41, 4 3 and 45 that are sensitive to diflFerent regions of the visible spectrum.
  • On support 40 is coated Color-Forming Unit 41 which comprises fogged silver halide emulsion 47 containing a magenta-forming DDR coupler and dispersed therein packets 46 comprising a silver halide emulsion that is sensitive to green light and contains a DIR coupler.
  • Over layer 41 is coated barrier layer 42 containing a compound capable of forming an insoluble salt with mercaptans.
  • Over layer 4-2 is coated a Color-Forming Unit, layer 43, that is sensitive to red light similar to that described for layer 41 except the fogged silver halide emulsion contain 'a cyan-forming DDR coupler and the packets comprise a silver halide emulsion sensitive to red light and a DIR coupler.
  • Over layer 43 is coated barrier layer 44 containing a compound capable of forming an insoluble salt with mercaptans and a yellow filtermaterial.
  • Over layer 44 is coated layer 45 which is a Color-Forming Unit sensitive to blue light similar to that described for layer 41 except that the fogged silver halide emulsion contains a yellow-forming DDR coupler and the packets comprise a silver halide emulsion sensitive to blue light and a DIR coupler.
  • Over photographic support are coated three Color-Forming Units of the invention that are sensitive to different regions of the spectrum.
  • Over support 50 is coated nucleated metal salt layer 51 containing a cyan-forming DDR coupler.
  • Over layer 51 is coated a silver halide emulsion that is sensitive to red light and a DIR coupler.
  • Over layer 52 is coated barrier layer 53 containing a compound capable of forming an insoluble salt with mercaptans.
  • Over layer 53 is coated nucleated metal .salt layer 54 containing a magenta-forming DDR coupler.
  • Over layer 54 is coated silver halide emulsion layer 55 that is sensitive to green light and DIR coupler.
  • Over layer 55 is coated barrier layer 56 containing a compound capable of forming an insoluble salt with mercaptans and a yellow filter material. Over layer 56 is coated nucleated metal salt layer 57 containing a yellow-forming DDR coupler. Over layer 57 is coated a silver halide emulsion layer 58 that is sensitive to blue light and a DIR coupler.
  • mordanted reception layer 61 containing a mordant for acid dyes.
  • stripping layer 62 that serves to separate mordanted reception layer 61 from the light-sensitive and coupler-containing layers.
  • stripping layer 22 On color development, the dilfusible acid dyes produced on reacting oxidized color developing agent with DDR couplers diifuse imagewise in register to morclanted reception layer 61. Thereafter, stripping layer 22, along with all layers coated thereover, can be readily removed leaving a positive color image on supported reception layer 61.
  • Over stripping layer 62 are coated layers 63 to 79 which correspond to layers 51 to 53 of FIG. 4, respectively described above.
  • DDR couplers of the invention to wit, nonditlusible coupler compounds that release or form diffusible acid dyes on coupling with the oxidation products of color developing agents.
  • Couplers I to X below are substituted in the coupling position with preformed 'ellow dyes that are split from the ballasted couplers and become ditfusible when said couplers react with oxidized color developers.
  • Couplers XI to XXIX below form difiusible cyan dyes. 1 hydroxy 4 stearoyloxymercuri 2 naphthoic acid.
  • Couplers XLH to XLVI below form diifusible yellow dyes.
  • C ONHCmHa Difiusible dyes are formed when the above listed (i.e., I to XLVI) non-diffusing couplers are employed in the process of the invention with well-known p-phenylenediamine, developing agents, e.g., N,N-diethyl-p-phenylenediamine, 2 amino 5 diethylamiuo toluene, N-ethyl-flmethanesulfonamidoethyl 3 methyl-4-a1ninoaniline, and other N,N-dialkyl-p-phenylenediarnine developing agents described by Bent et al., J.A.C.S. 73, 31003125 (1951).
  • developing agents e.g., N,N-diethyl-p-phenylenediamine, 2 amino 5 diethylamiuo toluene, N-ethyl-flmethanesulfonamido
  • Couplers XLVII to LV are nondifiusible couplers which can also be used in the process of our invention when the color developing agent is supplied with the alkali solubilizing function.
  • Couplers XLVII to L below form difiusible cyan dyes.
  • Couplers LIV and LV below form difiusible yellow dyes.
  • a diazonium solution consisting of 16 g. of 4-arnino-3-pentadecylphenol, 7 g. of isoamylnitrite, and 10 ml. of concentrated hydrochloric acid in 100 ml.
  • Couplers XXXIV, XXXV, XXXVI, XXXVII, and )OOCVIII were each prepared according to the procedure given for coupler XXXIII above using the appropriate intermediates.
  • the catalyst was filtered off and the solution poured into 500 ml. of water.
  • Triethyltrimesate A mixture of 37 g. of trimesic acid (proc. N. Dak. Acad. SC: 8, 54 (1954); CA (1955) 8898b), 100 ml. of ethyl alcohol, 50 ml. of benzene, and 1 ml. of concentrated H SO was refluxed through a 6" packed column surmounted by a Dean Stark water spouter for 24 hours after which time the residue was cooled and the solid which crystallized was filtered and dried.
  • trimesic acid proc. N. Dak. Acad. SC: 8, 54 (1954); CA (1955) 8898b
  • 100 ml. of ethyl alcohol 50 ml. of benzene
  • 1 ml. of concentrated H SO was refluxed through a 6" packed column surmounted by a Dean Stark water spouter for 24 hours after which time the residue was cooled and the solid which crystallized was filtered and dried.
  • the yield of the triester was 38 g., M.P. 133-5 C.
  • Coupler XLIII was prepared according to the procedure given for coupler )GJI above using the appropriate intermediates.
  • DIR development inhibitor releasing
  • the above coupler (LXXVI) is suitable for use in alkaline color developing solutions in which case the sensitive element used can contain the non-diffusing coupler (DDR) providing the diffusible dye in the spontaneously developable emulsion layer overcoated with the negative or light-sensitive silver halide emulsion layer.
  • DDR non-diffusing coupler
  • During development coupler LXXVI forms a non-diffusible dye in the region of negative development and the mercaptotetrazole compound splits 01f and inhibits development of the underlying emulsion in the negative region, the emulsion in the positive region develops and a diffusable dye is formed from the more reactive image forming coupler which dye transfers to the reception layer thus forming a transferred positive dye image.
  • R can be any of the moieties given immediately above such as 2-nitrophenyl, aminophenyl, acylamidophenyl, etc.

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Abstract

953,454. Photographic materials and developers for dye image production. KODAK Ltd. April 6, 1960 [April 6,1959; June 3,1959], No. 12109/60. Heading G2C. A support bears at least one light-sensitive silver halide emulsion layer having therein, or in an adjacent layer, either (a) a preformed development-inhibitor-releasing non-diffusible coupler, or (b) a non-preformed development-inhibitorreleasing coupler, the said couplers being capable of reaction with the oxidation product of a primary aromatic amino silver halide developing agent to form a dye and a compound capable of inhibiting the development of silver halide by the developing agent. Couplers stated to be of these types are described in numerous classes and subclasses with structural formulae in some instances, about 74 specific couplers are quoted and uses thereof include control of contrast, speed, grain and image sharpness, colour correction and formation of masking images. The claims also embrace processes wherein an exposed image is developed in the presence of one of the specified couplers and developer compositions comprising a primary aromatic amino developer and such a coupler from which the released inhibitor is a mercaptan. The term "coupler" includes colourless (i.e. competing) couplers. Example 1 describes two films having respectively the couplers 3-carboxymethyl-5- (4-dodecyloxyphenylazo) rhodanine and 1-hydroxy- 4-(4-beazotriazolyl azo) -N-[8-(2, 4-di-t-amylphenoxy)butyl] -2-naphthamide in layers underlying silver halide emulsion layers and a colour developing mixture thereof which is stated to produce an improvement in image sharpness as compared with a control, the images being of silver. Example 2 describes the production of red-sensitive films containing cyan-forming couplers overcoated with green-sensitive layers containing the development-inhibiting substances of the invention and reduction of gamma in the red-sensitive emulsions caused thereby. Examples 3, 4 are concerned with use of the couplers of the invention in developing solutions to control grain and contrast of silver and dye images respectively; Examples 5, 6 colour correction in multilayer films. Example 7 this in a multilayer packet film and Example 8 in a multilayer film including fogged emulsion layers. Example 9 reverts to the use of coupler in a developer, Example 10 describes use of the couplers to reduce grain size, and Examples 12, 13 transfer procedure using zinc sulphide nuclei layers. The light-sensitive materials which are claimed in Specification 932,272 comprising a support bearing a light-sensitive silver halide emulsion-layer, contiguous thereto a developable silver halide emulsion containing a non-diffusing colourant capable of reacting with oxidised developer. To form a diffusible colourant, and closely associated with the light-sensitive emulsion layer a compound (usually a coupler) containing a development inhibiting "moiety" (sic) capable of being split off by oxidised developer to form a diffusible development inhibitor is disclaimed. Specifications 680,488, 711,488, 755,655, 798,512, 840,731, 904,364 and 912,258 also are referred to.

Description

Jan. 4, 1966 Q A ETAL 3,227,551
PHOTOGRAPHIO COLOR REPRODUCTION PROCESS AND ELEMENT Filed Dec. 14, 1962 Fig./
2 Sheets-Sheet 1 PROTECTIVE LAYER AgX BLUE SENSITIVE EMULSION INH/BI TIN G COUPL ER FOGGED AgX+YELLOW-FORMlIV6 COUPLER BARR/ER LAYER AgX RED-SENSITIVE EMULSION l6 VIIIIJJIA. INHIBIT/N6 COUPLER l5 mwwmw F06650 Ag)! CYAN- FORM/N6 COUPLER /4 VIII. m BARR/ER LAYER /3 mm? Agx 6R. SENSITIVE EMULSION /2 INHIBIT/IVE COUPLER WWW FOGGED Agx +MA6E/WI4-FORM/IVG COUPLER SUPPORT 39 PROTECTIVE LAYER 38 INHIBIT/N6 COUPLER, AyX BL .-SENSITI|/E EMULSION 37 FOGGED AgX +YELLOW- FORM/N6 COUPLER 36 BARR/ER LAYER 35 INH/B/ T IN 6 COUPL E R, AgX R. SENSITIVE EMULSION FO66EDAgX1CYAN-EORM/N6 COUPLER BARR/ER LAYER INHIBIT/N6 COUPLER, AQX 6R. SENSITIVE EMULSION FOGGED AQX MAGENTA -FORMIN6 COUPLER SUPPORT PACKET 0F GREEN SENSITIVE A 9X 6 INHIBIT/N6 COUPLER FOGGED AgX AND COUPLER MAGENTA DYE CHARLES R. BARR JOHN WILLIAMS KEITH E WH/TMORE INVENTORS A T TORNE YS Jan. 4, 1966 c BARR ET AL 3,227,551
PHOTOGRAPHIC COLOR REPRODUCTION PROCESS AND ELEMENT Filed Dec. 14, 1962 2 Sheets-Sheet 2 Fig. 4
INHIBIT/N6 COUPLER, AgX R.SENS. EMULSION NUCLEATED METAL SALT+ CYAN FORMING COUPLER SUPPORT INHIBIT/N6 C OUPL ER, A 9X BL.- SENS. EMULSION 6 NUCLEATED METAL SALT-I-YELLOW-FORMINC COUPLER 68 BARRIER LAYER INHIBIT/N6 COUPLER, AgX 6R.-SENS. EMULSION 66 NUCLEATED METAL SALT+MACENTA-FORMIIV6 COUPLER BARRIER LAYER 64 INHIBIT/NC COUPLER, AgX R. SENS. EMULSION 53 NUCLEATED METAL SALT+ CYAIV-FORM/NG COUPLER 62 STR/PP/NG LAYER 5/ MORDANTED RECEPTION LAYER 6 SUPPORT CHARLES R BARR JOHN WILLIAMS KEITH E WH/ TMORE INVENTORS BY A ATTORNEYS United States Patent 3,227,551 PHOTOGRAPHIC COLOR REPRODUCTION PROCESS AND ELEMENT Charles R. Barr, John Williams, and Keith Whitmore,
Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Dec. 14, 1962, Ser. No. 244,774 21 Claims. (Cl. 96-3) This application is a continuation-in-part application of co-pending U.S. Serial No. 817,860 filed June 3, 1959 (now abandoned); U.S. Serial No. 126,782 filed June 29, 1961 (now abandoned); and US. Serial No. 126,783 filed June 29, 1961 (now abandoned). A
This invention relates to color photography, and more particularly, to photographic direct positive color diffusion transfer processes and photographic elements suitable for use in such processes.
Direct positive photographic color processes are well known in the art, and generally comprise a number of steps. A typical color process comprises such steps as a black-and-white development to form a negative image, a reversal exposure, development with an aromatic primary amino color developing agent to form insoluble image dyes in the areas of development, and a bleach step to remove developed silver. Color proceses are also known whereby color images are transferred to receiving elements, and which have the advantage of producing color images free of residual color couplers and other products of development. However, many of such processes of the latter type involve several complex steps, require several processing baths with large volumes of processing solutions, and produce poor quality color images due to lateral diffusion of dye-forming components.
It is an object of the present invention to provide a new color process in the photographic art.
It is another object of this invention to provide a new photographic process for producing sharp color images.
It is another object of this invention to provide a novel photographic diffusion transfer process wherein a dye image is transferred to a receiving layer,
It is another object of this invention to provide a novel color difiusion transfer process that can be efiected in one wet processing step.
It is another object of this invention to provide a novel color diffusion transfer process wherein the color development is carried out in the presence of a predominant proportion of the products of oxidation of'the color developing agent.
It is still another object of this invention to provide a novel process for preparing direct positive color images.
It is also an object of this invention to provide a novel color diffusion transfer process for producing direct positive full-color images.
It is likewise an object of this invention to provide a novel photographic element suitable for use in preparing direct positive color images by a photographic dittusion transfer process.
These and other objects are attained by means of this invention as described hereinafter with reference to preferred embodiments thereof.
The present invention concerns light-sensitive photographic elements having coated thereon at least two Color- Forming Units as described herein, and which elements can be processed in the presence of alkaline color developing solutions containing aromatic primary amino color developing agents to prepare direct positive color images.
The Color-Forming Units of the invention comprise:
Component A.A hydrophilic colloid-silver halide emulsion capable of recording latent images on exposure to light;
Component B.A photographic color coupler capable of forming a diffusible mercaptan development inhibitor on development with an alkaline color developing solution containing an aromatic primary amino color developing agent, such development inhibitor-releasing couplers being referred to herein as DIR couplers (this component can be either in the Color-Forming Unit or the color developing solution);
Component C.-An emulsion of a hydrophilic colloid and a water-insoluble metal salt developable to substantial density without exposure to light, and which is referred to herein as a spontaneously developable emulsion; and
Component D.--A nondifiusible photographic color coupler capable of forming a diftusible acid dye on development with an alkaline color developing solution containing an aromatic primary amino color developing agent, and which dittusible dye-releasing coupler is referred to herein as a DDR coupler,
When such Color-Forming Units are exposed, a latent image (negative image) pattern of developable silver halide is formed in the light-sensitive emulsion (Component A). When this exposed emulsion is developed in an alkaline color developing solution containing an aromatic primary amino color developing agent in the presence of a DIR coupler (Component B), the DIR coupler reacts with color development oxidation product to form a ditt'usible mercaptan development inhibitor. The resulting dilfusible developement inhibitor difiuses imagewise to the spontaneously developable emulsion (Component C) inhibiting development in regions corresponding to the latent image pattern (negative image area) formed in the light-sensitive emulsion. A DDR coupler (Component D) is contiguous to the developable metal salt of the spontaneously developable emulsion. The developable metal salt of the spontaneously developable emulsion in regions not inhibited against development by the diflusible development inhibitor (positive image area) develops and a ditfusible acid dye is formed in such regions when the DDR coupler reacts with color development oxidation product. The resulting acid dye diffuses imagewise in register to a juxtaposed reception layer containing a mordant for acid dyes to produce a positive color reproduction.
The Color-Forming Units are prepared so that the light-sensitive emulsion develops and a development inhibitor is released a finite time prior to the development of the spontaneously developable emulsion and the subsequent release of the ditfusible dye. Such can be accomplished by physically disposing the light-sensitive emulsion (Component A) and the contiguous DIR coupler (Component B) further from the support than the spontaneously developable emulsion, by utilizing a silver halide emulsion having a shorter development induction period for the light-sensitive emulsion than the developable metal salt in the spontaneously developable emulsion, and/or by utilizing DIR couplers that react at a faster rate than the DDR couplers.
The DDR couplers are integral components of the present elements while the DIR couplers can be either integral components or used in the alkaline color developing solution. As integral components of the elements, the DIR coupler can either be incorporated in, or in a layer contiguous to, the light-sensitive emulsion, and the DDR coupler can be either incorporated in, or in a layer contiguous to, the spontaneously developable emulsion.
lhotographic elements suitable for preparing correct full-color positive renditions can be prepared by utilizing three of the present Color-Forming Units wherein the light-sensitive emulsions are sensitive to red, green and 3 blue light respectively, and the DDR couplers are couplers capable of forming dir'fusible acid dyes complementary to the color of the spectral sensitivity of the respective Color-Forming Units. However, false sensitization can also be utilized in preparing the present photographic elements.
The DDR or difiusible dye-releasing couplers used in the photographic elements of the invention are initially nondiffusing in the layers of the element but form dyes diffusible in the layers of the element on reaction with oxidation product of aromatic primary amino silver halide photographic color developing agents. Such DDR couplers include those having the formulas:
DYE-LINK-(COUP-BALL), and BALL-LINK- COUP-SOL) n wherein:
1) DYE is a dye radical containing an acidic solubilizing radical;
(2) LINK is a connecting or linkage radical such as azo (N=N), azoxy mercuri (Hg), oxy (-O), alkylidene (includes both CH and =CH), monothio (-S), or dithio (SS);
(3) COUP is a photographic color coupler radical such as a S-pyrazolone coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, the coupler radical being substituted in the coupling position with the connecting or linkage radical;
(4) BALL is a photographically inert organic radical of such molecular size and configuration as to render the coupler nondiffusing in the element in the alkaline color developing solution;
(5) SOL is either a hydrogen atom or an acidic solubilizing group when the color developing agent contains an acidic solubilizing radical, SOL always being an acidic solubilizing radical when the color developing agent is free of an acidic solubilizing group; and
(6) n is an integer of l or 2 when LINK is an alkylidene radical, and n is always 1 when LINK is one of the other aforementioned connecting radicals, namely, azo, azoxy, mercuri, oxy, thio, or dithio.
The acidic solubilizing radicals attached to the diffusible dye-releasing (DDR) couplers described above can be solubilizing radicals which when attached to the coupler or developer moieties of the dies, render the dyes diffusible in the element in alkaline processing solutions. Typical of such radicals are carboxylic, sulfonic, ionizable sulfonamido, and hydroxy-substituted groups that lend to dyes negative charges.
Typical dye radical substituents (DYE) of the DDR couplers include azo, azomethine, indoaniline, indophenol, anthraquinone and related dye radicals Well known in the art that exhibit selective absorption in the visible spectrum. The dye radicals contain acidic solubilizing moieties.
When DDR couplers having the formula DYE-LINK- (COUP-BALL) as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a dilfusible preformed acid dye (DYE) is released which diffuses imagewise to a reception layer. An acidic solubilizing group on the preformed dye lends diffusibility and mordantability to the dye molecule. The coupling portion of the DDR coupler (COUP) couples with color developing agent oxidation product to form a dye that is nonditfusible in the element because of the attached ballasting group (BALL) in a noncoupling position. In this type of DDR coupler, the color of the diffusible dye is determined by the color of the preformed dye moiety (DYE), the color of the reaction product of color developer oxidation product and the coupler moiety (COUP) being unimportant to the color of the ditfusible image.
When DDR couplers having the formula BALL-LINK- (COUP-SOL) as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a ditfusible dye is formed with the color developing agent oxidation product and the coupling portion (COUP) of the DDR coupler which diffuses imagewise to a reception layer. Diffusibility is imparted to the dye by an acidic solubilizing group attached to a noncoupling position of the coupling portion (COUP) of the DDR coupler or to the color developing agent. The ballast portion of the DDR coupler remains im mobile. In this type of DDR coupler, the color of the diifusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COUP).
When the coupler radical (COUP) in the DDR couplers is a S-pyrazolone radical, we prefer to have substituted in the 3-position of the pyrazolone moiety an analino group or an alkoxy group. When the coupler radical (COUP) in the DDR couplers is a cyan-forming phenolic coupler radical, we prefer to have substituted in the ortho or 2-position of the phenolic moiety a fully substituted amido group (e.g.,
wherein R is an alkyl group or a phenyl group). Also, when the connecting radical (LINK) in the DDR couplers having the formula, BALL-LINK-(COUP-SOL) is an azo radical, we prefer that the ballasting radical (BALL) be a phenyl radical containing either a hydroxy group or an amino group (NH substituted in the ortho or 2-position of the phenyl moiety.
The DIR or development inhibitor-releasing couplers used in the photographic elements of the invention release or form development inhibitors that are ditfusi'ole in the layers of the Color-Forming Unit on reaction with oxidation product of aromatic primary amino silver halide photographic color developing agents. When the DIR couplers are utilized integral with the present photographic elements, ballasting groups are used to make the coupler nondifiusible in the layers of the Color-Forming Unit in alkaline color developing solutions. Such ballasted DIR couplers are preferred. When the DIR couplers are utilized in the color developing solution, the DIR couplers are free of ballasting groups and are ditfusible in the layers of the element in alkaline color developing solutions. DIR couplers of the invention include those having the formulas:
(BALL-COUP -LINK-MERC and (BALL) COUP-S-RAD wherein:
(1) BALL is a ballast group as described above for the DDR couplers;
(2) LINK is a connecting or linkage radical as described above for the DDR couplers;
(3) m is an integer of 0 or 1;
(4) n is an integer of 1 or 2 as described above for the DDR couplers;
(5) COUP is a photographic color coupler radical as described above for the DDR couplers;
(6) MERC is a ditfusible radical containing a mercapto radical (SH); and
(7) RAD is a photographically inert, ditfusible radical that forms a mercaptan with the monothio connecting or linkage radical (S).
A wide variety of photographically inert radicals that are diflfusible in the layers of the Color-Forming Unit and form mercaptans with the monothio connecting or linkage radical when the connecting radical is split on development can be used for the RAD substituent of the DIR couplers. Typical of such radicals are aryl, alkaryl and carbon-containing heterocyclic radicals. The aryl moiety of such radicals is preferably phenyl, and includes such substituents as nitro, lower alkyl, lower alkylamido, lower alkoxy, lower alkylsulfoamido, lower alkylcarbamyl, carbon-containing heterocyclic radicals and the like. The carbon-containing heterocyclic radicals, which can be attached directly to the monothio linkage radical or as a substituent on the described aryl moieties, generally contain at least one hetero nitrogen, oxygen or sulfur atom, and preferably, 1 to 4 hetero nitrogen atoms. The hetero nitrogen atoms in the heterocyclic radicals have no hydrogen atom attached thereto as the RAD radical is photographically inert. Illustrative carbon-containing heterocyclic radicals include l-phenyltetrazolyls, oxazolyls, oxadiazolyls, diazolyls, thiadiazolyls, henzoxazolyls, benzothiazolyls, pyrimidyls, pyridinyls, quinolinyls and the like.
MERC is a preformed mercapto development inhibiting moiety. A Wide variety of dilfusible radicals containing a mercapto radical (-SH) can be used for the MERC substituent of the DIR couplers. The mercapto radical can be suitably attached to an aryl, alkaryl or a carboncontaining heterocyclic radical such as RAD described above except that it is not necessary that the hetero nitrogen atoms on the heterocyclic radicals be free of hydrogen atoms.
When the DIR couplers are used integral with the photographic element, a ballast group (BALL) is utilized and m is l; and when the DIR couplers are used in the processing solution, such a ballast group is not utilized and m is 0. The DIR couplers containing preformed development-inhibiting moieties (MERC) are ballasted and always utilized integral with the photographic element. When DIR couplers are utilized in the processing solu tion, the spontaneously developable emulsions (Component C) are prepared to have longer development induction periods than the light-sensitive silver halide emulsrons.
When DIR couplers having the formula (BALL- COU?) -LINK-MERC are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a mercaptan development inhibitor (MERC) is released that is diffusible in the Color-Forming Unit. A ballasted or immobile dye is formed by reacting the coupler moiety (COUP) at the coupling position with oxidized color developing agent. The connecting radical (LINK) is preferably an azo (-N=N) or a monothio (-S) radical in this type of DIR coupler. As such DIR couplers are preformed development inhibitors, they are utilized in a layer adjacent to the light-sensitive silver halide emulsion layer of the present Color-Forming Units.
When DIR couplers having the formula (BALL) COUP-S-RAD are reacted with oxidized color developing agent, the connecting thio connecting or linkage radical (S) is split from the coupling position of the coupler moiety (COUP) and a merca-ptan development inhibitor is formed that is dilfusible in the Color-Forming Unit. When m is one, a ballasted or immobile dye is formed by reacting the coupler moiety (COUP) at the coupling position with oxidized color developing agent. When m is zero, a nonditrusible or a noumordantable dye is formed by reacting the coupler moiety (COUP) at the coupling position with oxidized color developing agent, both the DIR coupler and the color developing agent being free of acidic solubilizing groups when m is zero and the dye formed is difiusible. The substituent, in, is preferably one, and such DIR couplers can be utilized either in the light-sensitive emulsion or in a layer adjacent thereto in the present Color-Forming Units.
The nature of the ballast groups (BALL) in the DIR and DDR coupler compounds described above is not critical as long as they confer nondifiusibility to the coupler compounds. hereinafter in the specific couplers disclosed include long chain alkyl radicals or several short chain alkyl radicals Typical ballast groups exemplified having e.g., 8-22 carbon atoms, linked directly or indirectly to the coupler molecules, as well as aromatic radicals of the benzene and naphthalene series, etc., linked directly or indirectly to the coupler molecules by a splittable linkage, or by a removable or irremovable but otherwise nonfunctional linkage depending upon the nature of the coupler compound. Useful ballast groups generally have at least 8 carbon atoms.
Wtih regard to the above-described coupler radicals (COUP) in the DIR and DDR couplers, the coupling position is well known to those skilled in the photographic art. The S-pyrazolone coupler radicals couple at the carbon atom in the 4-position, the phenolic coupler radicals, including a-napthols, couple at the carbon atom in the 4-position and the open-chain ketomethylene coupler radicals couple at the carbon atom forming the methylene moiety (e.g.,
denoting the coupling position).
The term nondiffusing used herein as applied to the couplers and coupler reaction products, has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through organic colloid layers, such as gelatin, comprising the sensitive elements of the invention. The term dii'fusible as applied to the mercaptan development inhibitors released from the DIR couplers and the dyes released from the DDR couplers in the present processes has the converse meaning and denotes materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of the nondiifusing materials from which they are derived in alkaline color developing solutions.
The silver halide emulsions of the present photographic elements are conventional developing-out photographic silver halide emulsions including silver chloride, silver bromide, silver bromoiodide, silver chlorobromide and silver chlorobromoiodide emulsions. There can be em ployed as the dispersing agent or substrate for the silver halide in its preparation, gelatin or some other commonly employed photographic hydrophilic colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound, although gelatin is preferred. Such hydrophilic colloidal materialscan also be used in the non-light-sensitive layers in the subject elements in accordance with usual practice. Such hydrophilic collids are well known in the art.
The subject photographic emulsions can contain the addenda generally utilized in such products including optical sensitizers, speed-increasing materials, antifoggants, coating aids, gelatin hardeners, plasticizers, ultraviolet, absorbers and the like.
As described above, each Color-Forming Unit in the photographic elements of the invention contains, in addition to a light-sensitive silver halide emulsion (Component A), an emulsion of a water-insoluble metal salt that is developable (i.e., reducible to metal) with alkaline color developing solutions containing aromatic primary amino color developing agents to a substantial density without light exposure of the element (Component C). Such metal salts are preferably such Water-insoluble lightsensitive silver salts such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, silver citrate, silver oxalate, silver phosphate, silver stearate, silver ferrocyanide, silver cyanide, silver thiocyanate and the like. Other useful salts include palladium bromide, palladium cyanide and related heavy metal salts, as well as cuprous bromide and the like. Such metal salts can be made spontaneously developable by incorporating in the emulsion a wide variety of wellknown physical development nuclei. Typical development nuclei include colloidal noble metals such as silver and gold; colloidal metal sulfides, selcnides and tellurides such as lead sulfide, nickel sulfide, cadmium sulfide, silver sulfide, silver selenide, silver telluride, copper sulfide, zinc sulfide and mercury sulfide; metal proteinates such as silver proteinates; sodium sulfide; colloidal sulfur; and such organic sulfur compounds as thiourea, and xanthates. Conventional developer solvents for the metal salts are utilized in the developing compositions when the physical development nuclei are employed to make the emulsions spontaneously developable, including ammonium and alkali metal thiosulfates, thiocyanates, sulfites and the like. Another method that can be utilized to make the lightsensitive, Water-insoluble salts spontaneously developable is by prefogging the emulsion with light or with chemical reducing agents such as alkali metal borohydrides and the like in accordance with well-known photographic fogging techniques.
A wide variety of alkaline color developing solutions containing aromatic primary amino color developing agents can be utilized to process the present photographic elements. Such developing solutions are utilized to develop or reduce to silver the exposed silver halide in the light-sensitive emulsions (Component A) to form a negative image, and to develop or reduce to a metal the metal salt in the spontaneously developable emulsion (Component C) to form a positive image. Particularly useful developing agents are the well-known p-phenylenediamine color developing agents. The color developing agent can be either incorporated in an alkaline photographic developing solution that is topically applied to the present photographic elements on processing, or the color developing agent can be incorporated in the element.
When the color developing agent is used in the present photographic elements it is advantageous to use forms that have substantial stability in emulsions such as Schifi base derivatives of primary amino developing agents. Such Schiff bases are prepared by reacting primary amino developing agents with sulfonated, hydroxylated or carboxylated aromatic aldehydes of the benzene or naphthalene series. Such Schifi bases typically have the formula RN=CHR' wherein R is an aryl radical such as a phenyl radical substituted in the ortho or para position with a hydroxyl group or an amino group (e.g., Ol-l, NH NHR or N(R") wherein R" is a lower alkyl radical having 1 to 6 carbon atoms); and R is an aryl radical such as phenyl or naphthyl substituted with an acidic group such as carboxyl, sulfo, and hydroxy lower alkyl groups. A typical Schiff base color developing agent can be prepared by reacting 2-arnino-5-diethylaminotoluene and o-sulfobenzaldehyde. Other Schiff base developers that are useful as such, as salts or as sulfur dioxide complexes include:
(1) N ethyl-N-(fi-hydroxyethyl)-4-(o-sulfobenzylideneamino)aniline sodium salt,
(2) N,N diethyl-4-(2,4-dihydroxybenzylideneamino)-3- methylaniline, and
(3) N ethyl-3-methyl-N-(fi-methylsulfonamidoethyl)-4- (2-sulfobenzylideneamino)aniline sodium salt.
Such incorporated developing agents can be activated by immersing the photographic element in an aqueous alkaline solution or by spreading an aqueous alkaline solution on the surface of the element. Such incorporated developing agents can be positioned in any layer of the present photographic elements from which the developing agents can be readily made available for development on activation with aqueous alkaline solutions. Generally, such incorporated developing agents are either incorporated in the light-sensitive silver halide emulsion layers or in layers contiguous thereto.
Typical supports comprising the photographic elements of the invention include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, po1yethylene terephthalate film, polyethylene film, polypropylene film, and related films of resinous materials, as well as paper, glass, and others.
In preparing the photographic elements of the inven tion, the above-described emulsion layers are coated on the photographic supports in the form of multilayer color photographic elements having at least two and preferably three Color-Forming Units sensitive to different regions of the visible spectrum. The uppermost Color-Forming Unit is preferably selectively sensitive to blue light. Between the blue light-sensitive Color-Forming Unit and the other Color-Forming Units there is typically disposed a yellow dye layer or Carey Lea silver layer for absorbing or filtering blue radiation that may be transmitted through the uppermost blue sensitive layer. However, the physical disposition of the red, green and blue light-sensitive Color- Forrning Units within the present photographic elements can be Widely varied in accordance with usual practice. Such multilayer photographic elements can also have other interlayers or sublayers for specialized purposes in accordance with usual practice.
In another embodiment of the invention, each Color- Forming Unit can be a single layer. The DIR coupler and the light-sensitive silver halide emulsion (Component A) can be substantially uniformly dispersed in packets in the spontaneously developable emulsion containing the DDR coupler. Alternatively, the DDR coupler and the spontaneously developable emulsions can be substantially uniformly dispersed in packets in the lightsensitive silver halide emulsion containing the DIR coupler. Reference is made to Godowsky, U.S. Patent 2,698,794 and Van Campen et al., U.S. Patent 2,763,552 for suitable methods for preparing silver halide-color coupler packets and dispersing couplers. In such Color- Forming Units, the spontaneously developable emulsions are more generally prepared to have longer development induction periods than the light-sensitive silver halide emulsions. Alternatively, DIR couplers having faster reaction rates than the DDR couplers can be utilized in light-sensitive emulsion packets containing the DIR couplers.
Barrier layers are used between each Color-Forming Unit to ensure that the activity of the development inhibiting mercapto compounds released by the DIR couplers are confined to a single Color-Forming Unit. Hence, the barrier layers contain a water-insoluble salt or metal capable of forming a water-insoluble salt with mercaptans, silver halides such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., being preferably used. Other compounds suitable for use in the present barrier layers that react with mercaptans include colloidal metals such as silver and gold; and colloidal metal sulfides, selenides and tellurides such as lead sulfide, nickel sulfide, cadmium sulfide, silver sulfide, copper sulfide, zinc sulfide, mercury sulfide, silver selenide, silver telluride and the like. The barrier layers containing light-sensitive silver salts are prepared to be substantially less sensitive to light than the light-sensitive emulsions in the Color-Forming Units. Such barrier layers also serve to prevent oxidized color developing agent from wandering from one Color-Forming Unit to another where it could cause color contamina tion. Antioxidants such as n-octadecyl hydroquinone and the like phenolic antioxidants, and nondiifusible photographic color couplers that form nondifiusible dyes on coupling with oxidized aromatic amino color developing agents can be utilized in the barrier layers to prevent wandering of such oxidized color developing agent.
The reception layer used to receive the difiused dye images on color development of the photoelements of the invention can be either a separate sheet pressed in contact with the photoelement or a layer integral with the photoelement.
When the reception layer is a separate reception sheet, the development and transfer operations can be efiected by bathing either or both the exposed photographic element and the mordanted reception sheet in the developing solution before rolling into contact with each other.
Alternatively, a viscous developing composition can be placed between the elements for spreading in a predetermined amount across and in contact with the exposed surface of the sensitive element so as to provide all of the solution required for the picture area. The viscous developing composition is desirably utilized in one or more pods integral with the photoelement or the reception sheet that can be readily ruptured when development is desired, suitable viscous developer utilization techniques being disclosed in US. Patents 2,543,181; 2,559,643; 2,647,049; 2,647,056; 2,661,293; 2,698,244; 2,698,798; and 2,774,668.
When the reception layer for receiving the diffusible dye is an integral part of the photosensitive assembly it is also useful. A typical element of this type can comprise a support, a mordanted colloid layer thereon and the various emulsion layers described above coated thereover. When easily dissolved emulsions are used such as those containing polyvinyl alcohol or an alkali-soluble cellulose ether phthalate vehicles, or a wet or dry stripping layer containing such vehicles is provided between the emulsions and reception layer, the developed emulsion layers can then be readily separated from the reception layer leaving the dye image thereon. Similarly, the reception layer can be initially bonded to the outer emulsion surface. In this case, it is preferred to expose through the support of the sensitive element unless the reception layer itself is transparent. Such photoelements can be processed in the same manner as those not containing integral reception layers.
The reception layers in the photoelements of the invention can contain any of the conventional mordant materials for acid dyes. The reception layer can contain mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone described in the Minsk US. Patent 2,832,15 6 granted April 14, 1959. Other mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et al., US. Patent 2,484,430 granted October 11, 1949 and cetyl trimethylammonium bromide, etc. Particularly effective mordanting compositions are described in copending applications of Knechel et al., US. Serial No. 211,095 filed July 19, 1962, and Bush, US. Serial No. 211,094 filed July 19, 1962. The mordanting compositions described in the Knechel et al. application comprise at least one hydrophilic organic colloid containing a finely-divided, uniform dispersion of droplets or globules of a high-boiling, water-immiscible organic solvent in which is dissolved a high concentration of a cationic, nonpolyme'ric, organic dye-mordanting compound for acid dyes. The mordanting compositions described in the Bush application comprise at least one hydrophilic organic colloid containing a finely-divided, uniform dispersion of particles of a salt of an organic acidic compmition containing free acid moieties and a cationic, nonpolymeric, organic dyemordanting compound for acid dyes. Useful cationic or basic organic dye-mordanting compounds for acid dyes include quaternary ammonium and phosphonium, and ternary sulfonium compounds in which there is linked to the N, P, or S onium atom at least one hydrophobic ballast group such as long-chain alkyl or substituted alkyl groups. Furthermore, the reception layer or sheet can be sumcient by itself to mordant the dye as in the case of the use of a sheet or layer of a polyarnide or related polymeric material.
Reception sheets for the dye images, as well as the photoelements of the invention can contain ultraviolet absorbing materials. In the reception sheets, ultraviolet absorbers protect the mordanted dye images from fading and print-out due to ultraviolet light. In the photoelements, ultraviolet absorbers can serve as taking filters to reduce ultraviolet sensitivity. Typical ultraviolet absorbing materials are described in copending applications of Sawdey, U.S. Serial Nos. 144,228 filed October 10, 1961 and 183,417 filed March 29, 1962. Illustrative useful ultraviolet absorbing materials disclosed by Sawdey have the formulas wherein: R is a phenyl radical including such substituents as hydrogen atoms, halogen atoms, alkyl radicals, alkoxy radicals or hydroxy radicals; and R R and R are hydrogen atoms, halogen atoms, nitro radicals, alkyl radicals, alkoxy radicals, aryl radicals -or aryloxy radicals. Other ultraviolet absorbing materials well known in the photographic art can also be utilized.
If desired, a keep-negative as well as a positive color transfer print can be prepared. In preparing such a color negative, a conventional photographic color coupler of the type that forms a nondiifusible dye when reacted with oxidized color coupler is utilized with the DIR coupler. In this embodiment, DDR couplers are chosen that do not form colored nondiffusible dyes during the present process. Further, the DIR couplers are chosen so that the dyes which are formed are either diffusible or have absorptions similar to those of the respective keep-negative nondiffusible couplers. Also, the reception layer used to receive the diifused positive dye image is a separate receiving sheet not integral with the element. After the positive image is transferred to the receiving sheet, the remaining negative element is fixed in hypo to remove unexposed silver halide and bleached (i.e., with an alkali metal ferricyanide) to remove silver. Suitable photographic color coupl-ers that form nondifiusible dyes are of the phenolic, S-pyrazolone and open-chain ketomethylene type such as those disclosed in Spence et al., U.S. Patent 2,640,776; Weissberger et al., US. Patent 2,407,210; and Weissberger et al., US. Patent 2,474,293.
The drawings illustrate in section and in elevation typical photographic elements of the invention.
FIG. 1 illustrates a typical photographic element of the invention wherein the DIR or development inhibitorreleasing coupler is positioned in a layer contiguous to the light-sensitive silver halide emulsion and the spontaneously developable emulsion comprises a fogged silver halide emulsion in each Color-Forming Unit.
FIG. 2 illustrates a typical photographic element of the invention wherein the DIR coupler is positioned in the light-sensitive silver halide emulsion and the spontane ously developable emulsion comprises a fogged silver halide emulsion in each Color-Forming Unit.
FIG. 3 illustrates a typical photographic element of the invention in which each Color-Forming Unit is a single layer wherein packets of silver halide and the DIR coupler are dispersed in a fogged silver halide emulsion containing the DDR or diffusible dye-releasing couplers. FIG 3 includes an enlarged section of one Color- Forming Unit.
FIG. 4 illustrates a typical photographic element of the invention wherein the DIR coupler is positioned in the light-sensitive silver halide emulsion and the spontaneously developable emulsion comprises a nucleated metal salt in each Color-Forming Unit.
FIG. 5 illustrates a typical photographic element of the invention similar to that of FIG. 4 except that an integral mord-anted reception layer is present as well as a stripping layer to facilitate the removal of the Color- Forming Units after processing.
With respect to FIG. 1, on photographic support 10 are coated three Color-Forming Units of the invention that are sensitive to a different region of the visible spectrum. On support 10 is coated fogged silver halide emulsion layer 11 containing a magenta-forming DDR coupler. Over layer 11 is coated development-inhibiting layer 12 containing a DIR coupler. To complete the Color-Forming Unit nearest the support, silver halide R and R;
emulsion layer 13 that is sensitive to green light is coated over layer 12. Over the green-sensitive layer 13 is coated barrier layer 14 that contains a compound capable of forming an insoluble salt with mercaptans such as a silver halide. As described above, such barrier layers can contain antioxidants or nonditlusible color couplers that form insoluble dyes on reaction with oxidized color developing agent, such a-ddenda serving to minimize wandering of oxidized color developer and thu reducing color fog. Over barrier layer 14 is coated fogged silver halide emulsion layer 15 containing a cyan-forming DDR coupler. Over layer 15 is coated development inhibitor layer 16 containing a DIR coupler. To complete the second Color-Forming Unit, silver halide emulsion layer 17 that is sensitive to red light'is coated over layer 16. Barrier layer 18 containing a compound capable of forming an insoluble salt with mercaptans and a filter for blue light such as a yellow coupler, a yellow dye or Carey Lea silver is coated over layer 17. Over barrier layer 18 is coated fogged silver halide emulsion layer 19 containing a yellow-forming DDR coupler. Over layer 19 is coated development inhibiting layer 20 containing a DIR coupler. To complete the third Color-Forming Unit, silver halide emulsion layer 21 that is sensitive to blue light is coated over layer 20. A layer of a hydrophilic colloid such a protective layer 22 is coated on layer 21.
With respect to FIG. 2, on photographic support are coated three Color-Forming Units of the invention that are sensitive to different regions of the visible spectrum. On support 30 is coated fogged silver halide emulsion layer 31 containing a magenta-forming DDR coupler. Over layer 31 is coated silver halide emulsion layer 32 that is sensitive to green light and contains a DIR coupler. Over layer 32 is coated barrier layer 33 containing a compound capable of forming an insoluble salt with mercaptans. Over layer 33 is coated fogged silver halide emulsion layer 34 containing a cyan-forming DDR coupler. Over layer 34 is coated silver halide emulsion layer 35 that is sensitive to red light and contains a DIR coupler. Next, barrier layer 36 containing a compound capable of forming an insoluble salt with mercaptans and a yellow filter material is coated. Over layer 36 is coated fogged silver halide emulsion layer 37 containing a yellow-forming DDR coupler. Over layer 37 is coated silver halide emulsion layer 38 that is sensitive to blue light and contains a DIR coupler. Over layer 38 is coated protective layer 39.
In FIG. 3, each Color-Forming Unit comprises a single layer, namely layers 41, 4 3 and 45 that are sensitive to diflFerent regions of the visible spectrum. On support 40 is coated Color-Forming Unit 41 which comprises fogged silver halide emulsion 47 containing a magenta-forming DDR coupler and dispersed therein packets 46 comprising a silver halide emulsion that is sensitive to green light and contains a DIR coupler. Over layer 41 is coated barrier layer 42 containing a compound capable of forming an insoluble salt with mercaptans. Over layer 4-2 is coated a Color-Forming Unit, layer 43, that is sensitive to red light similar to that described for layer 41 except the fogged silver halide emulsion contain 'a cyan-forming DDR coupler and the packets comprise a silver halide emulsion sensitive to red light and a DIR coupler. Over layer 43 is coated barrier layer 44 containing a compound capable of forming an insoluble salt with mercaptans and a yellow filtermaterial. Over layer 44 is coated layer 45 which is a Color-Forming Unit sensitive to blue light similar to that described for layer 41 except that the fogged silver halide emulsion contains a yellow-forming DDR coupler and the packets comprise a silver halide emulsion sensitive to blue light and a DIR coupler.
In FIG. 4, over photographic support are coated three Color-Forming Units of the invention that are sensitive to different regions of the spectrum. Over support 50 is coated nucleated metal salt layer 51 containing a cyan-forming DDR coupler. Over layer 51 is coated a silver halide emulsion that is sensitive to red light and a DIR coupler. Over layer 52 is coated barrier layer 53 containing a compound capable of forming an insoluble salt with mercaptans. Over layer 53 is coated nucleated metal .salt layer 54 containing a magenta-forming DDR coupler. Over layer 54 is coated silver halide emulsion layer 55 that is sensitive to green light and DIR coupler. Over layer 55 is coated barrier layer 56 containing a compound capable of forming an insoluble salt with mercaptans and a yellow filter material. Over layer 56 is coated nucleated metal salt layer 57 containing a yellow-forming DDR coupler. Over layer 57 is coated a silver halide emulsion layer 58 that is sensitive to blue light and a DIR coupler.
With respect to FIG. 5, on photographic support 60 is coated mordanted reception layer 61 containing a mordant for acid dyes. Over layer 61 is coated stripping layer 62 that serves to separate mordanted reception layer 61 from the light-sensitive and coupler-containing layers. On color development, the dilfusible acid dyes produced on reacting oxidized color developing agent with DDR couplers diifuse imagewise in register to morclanted reception layer 61. Thereafter, stripping layer 22, along with all layers coated thereover, can be readily removed leaving a positive color image on supported reception layer 61. Over stripping layer 62 are coated layers 63 to 79 which correspond to layers 51 to 53 of FIG. 4, respectively described above.
The following are representative DDR couplers of the invention, to wit, nonditlusible coupler compounds that release or form diffusible acid dyes on coupling with the oxidation products of color developing agents.
Couplers I to X below are substituted in the coupling position with preformed 'ellow dyes that are split from the ballasted couplers and become ditfusible when said couplers react with oxidized color developers.
l-hydroxy-4-{3-[4-(N-ethyl-N ,8 sulfoethylamino)2- l-hydroxy-4-{4-[1-(4-sulfophenyl) 3 methyl-4pyrazol-S-onylazo]-3-sulfophenylazo}-N-[5-(2,4 di tertamylphenoxy)-butyl]-2-naphthamide disodium salt.
CH3 SOaNa- C l N N-CH "-QSO Na 0 II o on {3 [a (2, 4 di tert amylphenoxy)acetamido] benzoyl} a. {3 [4 (N ethyl N ,8 sulfoethylamino) 2 methylphenylazo]phenylazo} 2 methoxyacetanilide sodium salt.
0 0 3110 ONH (t) 05111 1 -oo112o ONE 1% Q 1 hydroxy 4 {4 [1 (4 sulfophenyl) 3 carboxy 4 pyrazol 5 onyl azo] 3 sulfophenylazo}- N {4 [a (2, 4 di tert amylphenoxy) butyramido] 45 phenethyl} 2 naphthamide.
OCH:
pling position as a direct result of said coupling reaction. Couplers XI to XXIX below form difiusible cyan dyes. 1 hydroxy 4 stearoyloxymercuri 2 naphthoic acid.
23 Couplers XLH to XLVI below form diifusible yellow dyes.
a-Benzoyl-u-(4-hydroxy 2-pentadecylphenylazo) 4 (3-su1fobenzamido)acetanilide sodium salt.
a-Benzoy1-a-(4 hydroxy-Z pentadecylphenylazo) 4- (3,5-disulfobenzamido)acetanilide dipotassium salt.
XLIII. 803K I II II $03K N -C15Hai a-Benzoyl-u-[4 3-methyl 5 pentadecyl)pyrazolylazo]-4 (3,5 disulfobenzamido)acetanilide dipotassium salt.
a-Benzoy1-a-(3 octadecylcarbamylphenylthio) 3,5 dicarboxyacetanilide.
XLV. COOH II CaHsC-fiH-C-NH I C O OH C ONHCmHa a-Pivalyl-a-( 3 octadecylcarbamylphenylthio) 4-sulfoacetanilide potassium salt.
XLVI.
C ONHCmHa Difiusible dyes are formed when the above listed (i.e., I to XLVI) non-diffusing couplers are employed in the process of the invention with well-known p-phenylenediamine, developing agents, e.g., N,N-diethyl-p-phenylenediamine, 2 amino 5 diethylamiuo toluene, N-ethyl-flmethanesulfonamidoethyl 3 methyl-4-a1ninoaniline, and other N,N-dialkyl-p-phenylenediarnine developing agents described by Bent et al., J.A.C.S. 73, 31003125 (1951).
Couplers XLVII to LV are nondifiusible couplers which can also be used in the process of our invention when the color developing agent is supplied with the alkali solubilizing function.
Couplers XLVII to L below form difiusible cyan dyes.
l-hydroxy-4- (4-0ct adecyloxyphenylazo -N-methyl 2- naphthanilide.
XLVII. OH
1-hydroxy-4-dodecyloxy-Z-naphthanilide.
XLVIII. (|)H I 0 C l2 25 1-hydroxy-4-(2-amino 4 octadecylphenylazoxy) 2- naphthamide.
XLIX. (DH
@ o 0 NH,
s: IMO
I CISHST 1-hydroxy-2',5'-dibutoXy-4 [4 (sulfomethyl)phenylazo]-2-naphthanilide.
L. (|)H (|)C4Hn I O C4119 I N II i I CHZSOSH 25 Couplers LI to LIlI below form difiusible magenta dyes.
1-phenyl-3-methyl-4-(4- octadecyloxybenzylidene) 5- pyrazolone.
0-0 isHar 4,4-thiobis 1-phenyl-3-methyl-5-pyrazolone) Couplers LIV and LV below form difiusible yellow dyes.
oc,0:.'-(4 octadecyl0xybenzy1idene)bis[a benzoylacetanilide].
LIV. O O
HTQ-O 0131131 Qt t Q a,a-Dithiobisbenzoylacetanilide.
LV. 0 O
When the DDR couplers given above were incorporated into exposed silver halide emulsions that were developed in contact with a mordanted reception layer using an alkaline color developing composition containing the developing agent 4-amino-N-ethy1-N-(fi-hydroxyethyl) on the reception layer from the respective couplers:
Coupler:
I Yellow.
II Do. III Do:
IV Orange-yellow. V Yellow.
VI Do.
VII Do. VIII Do. IX Do.
X Do. XI Cyan. XII Do. XIII Do.
XIV Do.
XV Do. XVI Do. XVII Do. XVIII Do. XIX Do. XX Do. XXI Do. XXH Do. XXIII Do. XXIV Do. XXV Do. XXVI Do. XXVII Do. XXVIII Do. XXIX Do. XXX Magenta. XXXI Do. XXXH Do- XXXIII Do. XXXIV Do. XXXV Do. XXXVI Do. XXXVII Do. XPQiVIII Do. XXXIX Do. XL Do. XLI Do. XLII Yellow. XLHI Do. XLIV Do.
XLV Do.
PGJVI Do.
The following syntheses illustrate the methods for preparations of representative DDR couplers of our invention.
COUPLER I 1 hydroxy 4 {3 [4 (N ethyl N B sulfoethylamino) 2 methylphenylazo]phenylazo} N [8(2,4 di-tert-amylphenoxy)butyl]-2-naphthamide sodium salt To 200 ml. of concentrated sulfuric acid at 10 C. was added with stirring 17 g. of Intermediate C below. To the resultant solution was added dropwise over a period of 30 minutes at 5 C. with stirring a solution of 3.5 g.
of sodium nitrite in 35 ml. of concentrated sulfuric acid (i.e. nitrosylsulfuric acid solution). This solution was stirred for a total of two hours after which time it was poured onto crushed ice. This solution was then added to a solution of 21 g. of 'l-hydroxy-N- [6(2,4-di-tertamylphenoxy)butyl]-2-naphthamide (US. Patent 2,474,- 293), in two liters of pyridine over a 30-minute period with stirring at 05 C. After 12 hours at room temperature the reaction mixture was mixed with 1.5 kg. of crushed ice and acidified with concentrated hydrochloric acid. The red solid which separated was collected, washed with water and recrystallized twice from glacial acetic acid, yielding the product.
a; 42.7 COUPLER I, INTERMEDIATE A N-ethyl-3-methyl-N-(fi-sulfoethyl) aniline sodium salt COUPLER I, INTERMEDIATE B p {N ethyl N [3 methyl 4 (3 nitrophenylazo) phenyl] amino}-ethylsalfnic acid sodium salt To a solution of 27 g. of Intermediate A above in 250 ml. of water at 0 C. was added a chilled diazonium solution consisting of 14 g. of m-nitroaniline and 7.5 g. of sodium nitrite in 200 ml. of 6 N hydrochloric acid. The resultant mixture was neutralized to Congo red paper by the addition of sodium acetate. This mixture was chilled for 2 hours after which time the solid which separated was collected, washed with cold water, and recrystalized from 360 ml. of water, yielding a green product.
COUPLER I, INTERMEDIATE C B {N [4 (3 aminophenylazo) 3 methy'lphenyl] N-ethylamin0}ethyl sulfonic acid sodium salt To a solution of 41 g. of Intermediate B above in 2 liters of water at 90 C. was added over a period of 30 minutes a solution of 40 g. of 60% sodium sulfide in 150 ml. of water. The mixture was refluxed for an additional 2 /2 hours during which time approximately /2 of the water was distilled oif. This mixture was filtered and refrigerated over night during which time a solid separated. The solid was collected and recrystallized from 200 ml. of ethyl alcohol, yielding the product.
COUPLER VII J-hydroxy-4-{4-[3 methyl 4 (1,S-disulfo-S-naphthylazo) 1 pyrazol 5 0nyl]phenylaz0} N [6 (3 pentadecylphenoxfibutyl] 2 naphthamide disodium salt A solution of 6.5 g. of sodium nitrite in 93 ml. of water was added to a solution of 49.5 g. of Intermediate E below in 300 ml. of five percent sodium carbonate solution. This mixture was cooled to 10 C. and added to a well-stirred mixture of 75 ml. concentrated hydrochloric acid and 150 g. of ice. After 1 /2 hours, the diazonium suspension was added in portions with vigorous stirring to a solution of 44.4 g. of Intermediate C below in a mixture of 1500 ml. of ethyl alcohol and 55 g. of potassium carbonate in 360 ml. Water. After two hours, the crude product was filtered, triturated in boiling ethyl alcohol, then dissolved in 1500 ml. ethyl alcohol and 1500 ml. of 3% potassium carbonate solution. The dark orange solution was filtered and acidified with acetic acid. The solid which separated was filtered, triturated in acetone and benzene, extracted twice with hot water, and recrystallized from a 1:1 n-propyl alcohol-water mixture, yielding 40 g. of product, M.P. 270 C.
COUPLER VH, INTERMEDIATE A y-(3-pemadecylphenoxy)butyronitrile A mixture of 4 g. of sodium hydroxide and 31 g. of 3-pentadecylphenol (Minn. Mining and Mfg. Co.) in 100 ml. of xylene was refluxed for 6 hours during which time 1.8 ml. of Water was distilled off. To the mixture was added 11 g. of 'y-chlorobutyronitrile dropwise over 1 hour after which time the mixture was refluxed for 7 hours. The xylene was then distilled off over a 12 hour period and the residual oil was poured into 25 ml. of dilute hydrochloric acid. The Waxy solid which separated was collected and recrystallized from ml. of acetonitrile, yielding 23 g. of product, M.P. 46-47 C.
COUPLER VII, INTERMEDIATE B 6( 3 -pentadecylphen0xy) butylamine A mixture of 5 g. of Intermediate A above, 3 ml. of ethyl-alcohol, 5 ml. of liquid anhydrous ammonia and 0.1 g. of Raney nickel was heated for 12 hours at 100 C. under a hydrogen atmosphere at a pressure of 2200 p.s.i. The cooled solution was filtered and concentrated in vacuo. The residual oil was distilled at 165 C. at 9 microns, yielding the product.
COUPLER VH, INTERMEDIATE C 1 -hydroxy-N-[6(3-pentadecylphen0xy)butyl] -2- naphrhamide A mixture of 5 g. of phenyl 1-hydroxy-2-naphthoate and 7 g. of Intermediate B above was heated at 150 C. for /2 hour in vacuo during which time phenol was collected from the mixture. The residual oil was poured into 100 ml. of petroleum ether whereupon a crystalline solid separated. This solid was collected and recrystallized from 90 ml. of ethyl alcohol, yielding 8 g. of product, M.P. 64-66 C.
COUPLER VII, INTERMEDIATE D (4-nitrophenyl) -3-methyl-4- (1,5-disulf0-3- naphthylazo)-5-pyraz0lone disodium salt To a solution of 2.8 g. of l-(4-nitrophenyl)-3-methyl- 5-pyrazolone, 0.5 g. of sodium hydroxide and 7 g. of sodium acetate in 40 ml. of water was added at 20 C. over a period of 20 minutes a diazonium mixture consisting of 1.1 g. of 2-amino-1,5-naphthalenedisulfonic acid disodium salt, 1.4 g. of sodium nitrite, 2 ml. of concentrated sulfuric acid and 10 ml. of water. The mixture was stirred for 1 hour at room temperature and heated over steam until all solids dissolved. The solution was cooled to 5 C. whereupon a red solid separated and was collected, yielding 45 g. of product.
COUPLER VII, INTERMEDIATE E 1 (4-amin0phenyl) -3-methyl4- (1,5-disulf0-3- naphthylazo) -5-pyraz0l0ne disodium salt To a mixture of 31 g. of Intermediate D above in 32 ml. of water at 90 C. was added over a period of 20 minutes a solution of 18 g. of 60% sodium sulfide in- 40 ml. of water. The mixture was heated at reflux for an additional 2 hours after which time it was cooled to 50 C. and acidified with acetic acid. The solid which separated was collected and recrystallized from 250 ml. of 10% brine solution, yielding 15 g. of product, M.P. 250 C.
COUPLER XI 1-hydroxy-4-steafoyloxymercuri-Z-naphthoic acid To a solution of 9.4 g. of l-hydroxy-Z-naphthoic acid (I.A.C.S. 64, 799 (1942)) in 200 ml. of dioxane was added a solution of 38 g. of mercuric stearate in 500 ml. of dioxane. The mixture was heated over steam for 5 hours during which time a white solid separated. This solid was collected, washed with hot methyl alcohol and dried, yielding 30 g. of product.
COUPLER XII 1-hydr0xy-4-d0decyloxy-Z-naphthoic acid To a suspension of 2 g. of 1,4-dihydroxy-2-naphthoic acid (I.A.C.S. 64, 799 (1942)) in 40 g. of lauryl alcohol was added dry hydrogen chloride gas at 90 C. over a period of 11 hours while stirring. The clear reaction mixture was left at room temperature over night during which time a white solid separated. This solid was filtered, slurried in 50 volumes of petroleum ether, refiltered and dried, yielding 1.25 g. of product, M.P. 136 C.
29 COUPLER XV 1 -hydroxy-N- fi-sulfoethyl -4- (4-0ctadecyloxyphenylazo) -2-naphthamide potassium salt To a solution of 51 g. of potassium hydroxide and 63 g. of Intermediate A below in 350 ml. of water and 1700 ml. of ethyl alcohol was added at 5 C. over a period of 1 hour, a diazonium solution consisting of 72 g. of Intermediate B below, 120 g. of p-toluene sulfonic acid, and 30 g. of isoamylnitrite in 2 liters of n-propyl alcohol. The mixture was stirred at room temperature for 5 hours after Which time 3 liters of water were added and the mixture brought to reflux. The hot solution was filtered, acidified with glacial acetic acid and'cooled whereupon a solid separated. The solid was collected, recrystallized from 1.5 liters of n-butyl alcohol, yielding 80 g. of product, M.P. 22830 C.
COUPLER XV, INTERMEDIATE A 1-hydroxy-N-(jS-sulfoethyl)-2-naphthamide potassium salt A mixture of 132 g. of phenyl l-hydroxy-Z-naphthoate, 1 liter of ethyl alcohol, 57.5 g. of taurine, 300 ml. of water and 28 g. of potassium hydroxide was refluxed for 15 hours after which time the solution was cooled and the solid which separated was collected, washed with ethyl alcohol, recrystallized from H and dried, yielding 71 g. of product, M.P. 284286 C.
COUPLER XV, INTERMEDIATE B 4-0ctadecyl0xyaniline A mixture of 39 g. of 4-nitrophenyloctadecyl ether (I.A.C.S. 73, 458 (1951)) and 0.5 g. of 10% palladium on charcoal in 300 ml. of ethyl alcohol was heated at 50 C. for /2 hour under a hydrogen atmosphere at a pressure of 50 psi.
The catalyst was filtered from the hot solution which was then chilled whereupon a solid separated. This solid was collected, and dried, yielding 32 g. of product, M.P. 7 881 C.
The preparations for couplers XVHI, XD(, XX, and XXI are given in copending application U.S. Serial No.
154,841, filed Nov. 24, 1961.
COUPLER XXIV 2- (3,5-disulf0benzam ido) -4- (4-hydroxy-2-pentadecylplzenylazo) --m ethylphenol dipotassium salt To a solution of 21 g. of 2-(3,5-dichlorosulfonylbenz amido)-5-methylphenol in 50 ml. of pyridine and 10 ml. of water was added a diazonium solution consisting of 16 g. of 4-arnino-3-pentadecylphenol, 7 g. of isoamylnitrite, and 10 ml. of concentrated hydrochloric acid in 100 ml. of n-propyl alcohol.- The mixture was stirred at room temperature for 12 hours after which time it was poured into 400 ml. of saturated potassuim chloride solution. The gummy solid which separated was collected, triturated twice in methyl alcohol and dried, yielding 11 g. of product.
COUPLER XXX 1-plzenyl-3- (3-sulfobenzamid0) -4- (4-0ctadecyl0xyphenylazo -5-pyraz0l0ne sodium salt To a solution of 3.6 g. of Intermediate B below and 2 g. of sodium hydroxide in 55 ml. of 90% ethyl alcohol at 0 C. was added with stirring a diazonium solution consisting of 3.6 g. of 4-octadecyloxyaniline (Intermediate B of Coupler XV above), 5.7 g of p-toluenesulfonic acid monohydrate and 1.5 g. of isoamylnitn'te in 100 ml. of n-propyl alcohol at 20 C. The mixture was stirred at room temperature for 3 hours after which time 25 ml. of water was added and the mixture was acidified with acetic acid. To this solution at 90 C. was added 100 g. of
sodium chloride and the resultant solution was filtered and cooled. The solid which separated was collected, washed with water and dried, yielding 6 g. of product, M.P. 198200 C.
COUPLER XXX, INTERMEDIATE A 1-phenyl-3-(3-chl0r0sulfonylbenzamido)-5-pyraz0l0ne To a solution of 88 g, of 1-phenyl-3-amino-5-pyrazolone in 400 m1. of diethyl oxalate at 90 C. was added with stirring 120 g. of m-chlorosulfonylbenzoyl chloride. The mixture was heated for /2 hour, cooled to 20 C. and the solid which separated was collected, triturated in water, ethyl acetate and dried, yielding 98 g. of product, M.P. 176177 C.
COUPLER XXX, INTERMEDIATE B 1-phenyl-3-(3-sulf0benzamido) -5-pyraz0l0ne COUPLER )QQGH 1-phenyl-3- (3,5-dz'sulf0benzamido) -4- (4-hydr0xy-2-pentadecylphenylazo) -5-pyraz0l0ne dipotassium salt To a solution of 5 g. of 1-phenyl-3-(3,5-disulfobenzamido)-5-pyrazolone dipotassium salt (prepared according to the procedure given for Intermediate B, coupler XXX above using the appropriate intermediates) in 20 ml. of 50% pyridine was added at 20 C. a diazonium solution consisting of 3 g. of 4-amino-3-pentadecylphenol, 1.5 g. of isoamylnitrite and 2 g. of concentrated hydrochloric acid in 20 ml. of n-propyl alcohol. The resultant mixture was stirred at room temperature for 12 hours after which time it was poured into 100 ml. of saturated potassium chloride solution. The solid which separated was collected, and recrystallized from 50 ml. of 60% ethyl alcohol, yielding the product.
Couplers XXXIV, XXXV, XXXVI, XXXVII, and )OOCVIII were each prepared according to the procedure given for coupler XXXIII above using the appropriate intermediates.
COUPLER XXXIX 1- [4-(3,5-dicarb0xybenzamid0) phenyl] -3-eth0xy-4- (3- octadecylcarbamylpheny lthio) -5pyraz0l0ne A mixture of 7.8 g. of Intermediate H below, 25 ml. of ethyl alcohol, 15 ml. of 2 N aqueous NaOH, and 35 ml. of water was stirred at 85 C. for 15 minutes. The solution was cooled to room temperature and acidified with 1:2 concentrated HCl-water.
The solid which separated was filtered off, washed with water, acetonitrile, and recrystallized from meth anol, yielding 4 g. of product,- M.P ZOO-202 C.
COUPLER XXXIX, INTERMEDIATE A 1-(4-nz'trophenyl)-3-eth0xy-5-pyraz0l0ne A mixture of 31 g. of 4-nitrophenylhydrazine, 100 ml. of ethyl alcohol, and 38 g. of ethyl-B,fi-diethoxyacrylate was refluxed for /2 hour. A solution of sodium ethoxide (prepared from 4.6 g. of sodium and 100 ml. of ethyl alcohol) was added and refluxed for another 20 minutes. This solution was acidified with glacial acetic acid and the solid which separated was filtered off, and recrystallized from 250 ml. of n-butyl alcohol, yielding 31 g. of product, M.P. 153-4 C.
31 COUPLER XXXIX, INTERMEDIATE B A mixture of 15 g. of Intermediate A above in 150 ml. of ethyl alcohol was reduced using Pd/Charcoal at 50 p.s.i., hydrogen pressure.
The catalyst was filtered off and the solution poured into 500 ml. of water.
The product was filtered oil and air dried, yielding 8.2 g. of product, M.P. 121122 C.
COUPLER XXXIX, INTERMEDIATE C Triethyltrimesate A mixture of 37 g. of trimesic acid (proc. N. Dak. Acad. SC: 8, 54 (1954); CA (1955) 8898b), 100 ml. of ethyl alcohol, 50 ml. of benzene, and 1 ml. of concentrated H SO was refluxed through a 6" packed column surmounted by a Dean Stark water spouter for 24 hours after which time the residue was cooled and the solid which crystallized was filtered and dried.
The yield of the triester was 38 g., M.P. 133-5 C.
COUPLER XXXIX, INTERMEDIATE D Diethyl ester of trimesic acid (3,5-dicarbethxybenz0ic acid) To a solution of 147 g. of the Intermediate C above in 2 liters of ethyl alcohol was added with stirring 250 ml. of 2 N NaOH in 500 ml. of ethyl alcohol. This mixture was refluxed for 30 minutes and stirred at room temperature for 12 hours, during which time a solid separated. This solid was filtered otf and recrystallized from a mixture of 500 ml. of ethyl alcohol and 500 ml. of water, yielding 80 g. of product, M.P. 153-5 C.
COUPLER XXXIX, INTERMEDIATE E 3,5-dicarbetlzoxybenz0yl chloride A mixture of 300 g. of Intermediate D above and 2 liters of thionyl chloride was refluxed for 2 hours, after which time it was concentrated in vacuo.
To the residue was added 250 ml. of dry benzene and again concentrated in vacuo.
The acid chloride thus formed was used as such in preparing Intermediate F below.
COUPLER XXXIX, INTERMEDIATE -F 1 [4-(3,5-dicarbethoxybenzamido) phenyl] -3-eth0xy- -pyraz0lon1e A mixture of 6.6 g. of Intermediate B above and 8.5 g. of Intermediate E above and 100 ml. of dry acetonitrile was refluxed for 5 hours. The mixture Was cooled to room temperature and the solid was filtered ofi, dried, and recrystallized from glacial acetic acid, yielding g. of product, M.P. 200-201 C.
COUPLER XXXIX, INTERMEDIATE G 3-octadecylcarbamylplaenylsulfenyl chloride Into a suspension of 8 g. of 3,3'-dioctadecylcarbamyldiphenyldisulfide (Loria et al. US. patent application Ser. No. 154,841, filed Nov. 24, 1961) in 120 ml. of anhydrous carbon tetrachloride was bubbled dry chlorine gas for 1 /2 hours at room temperature, during which time all of the solid dissolved and a clear light yellow solution was formed. The solution was concentrated in vacuo to a volume of 50 ml. to remove excess chlorine.
This solution of the sulfenyl chloride was used as such in the following reaction (i.-e., Intermediate H below).
COUPLER XXXD(, INTERMEDIATE Hv 1 [4- (3,5 -d icarbetlzoxy benzamido) plzenyl -3 -eth0xy-4- (3 -0ctadecyl carbamyl phenyl th i0 -5 -pyraz0lone A mixture of Intermediate G above and 9.35 g. of Intermediate F above in 200 ml. of dry dioxane was stirred at room temperature for 2 hours, heated to reflux for 1 hour, and concentrated in vacuo.
The residue was recrystallized from ethyl alcohol, yielding 8.5 g. of product, M.P. 1568 C.
COUPLER XL 1-(4-sulf0plzenyl) -3- (4-sulf0anilin0) -4-(3-octadecylcarbamylplzenylthio)-5-pyraz0lone disodium salt A suspension of 25 g. of Intermediate B below in 100 ml. of ethyl alcohol and 200 ml. of 2% aqueous NaOH was stirred at room temperature for /2 hour, during which time all solid dissolved. The solution was cooled and acidified with 5 ml. of acetic acid and concentrated in vacuo.
The crude solid residue was recrystallized from methyl alcohol, yielding 10 g. of product, M.P. 250 C.
COUPLER XL, INTERMEDIATE A COUPLER XL, INTERMEDIATE B A mixture of Intermediate G of Coupler XXXIX above (prepared from 24.5 g. of the disulfide) and 25 g. of Intermediate A above in 320 ml. of dry carbon tetrachloride was stirred at 55 C. for 12 hours.
The solution was then concentrated in vacuo and the residue was recrystallized from 300 ml. of ethyl acetate yielding 25 g. of product, M.P. 209-11 C.
COUPLER XLI 4,4'-(4-0ctadecyloxybenzylidene) bis [1 -.pllenyl-3- (3,5 -disulfobenzamido 5-pyraz0l0ne] tetrapotassium salt To a refluxing solution of 5.2 g. of 1-phenyl-3-(3,5-disulfobenzamido)-5-pyrazolone dipotassium salt in 45 ml. of ethyl alcohol and 20 ml. of water was added a solution of 1.9 g. of Intermediate A below and 0.5 g. of piperidine in 35 m1. of ethyl alcohol. The solution was refluxed for /2 hour and cooled to room temperature. The solid which separated was collected, recrystallized from ethyl alcohol, yielding 5 g. of product.
COUPLER XLI, INTERMEDIATE A 4 octadecyloxybenzaldehyde To a solution of 23 g. of sodium metal and 122 g. of 4-hydroxybenzaldehyde in 500 ml. of ethyl alcohol was added 333 g. of l-bromooctadecane. The mixture was refluxed with stirring for 20 hours during which time a solid separated. This solid was filtered and the filtrate was concentrated in vacuo. The residual material was then distilled at 253 C. at 1 mm. pressure, yielding 250 g. of product. I
COUPLER XLII 'a-Benzoyl-u-(4-hydr02qy-2-pentadecylphenylaz0)-4-(3- sulfobenzamia'o) acetanilide sodium salt To a solution of 4.5 g. of a-benzoyl-4-(3-chlorosulfonylbenzamido) acetanilide in 12 ml. of 90% pyridine was added .at 20 C. a diazonium mixture consisting of 3.2 g. of 4-amino-3-pentadecylphenol, 1.4 g. of isoamylnitrite and 2 ml. of cone. hydrochloric acid in 20 ml. of n-propyl alcohol. The resultant solution was stirred at room temperature for 12 hours after which time it was poured into 50 ml. of saturated sodium chloride solution. The yellow solid which separated was collected, and recrystallized twice from ethyl alcohol, yielding 2.2 g. of product.
Coupler XLIII was prepared according to the procedure given for coupler )GJI above using the appropriate intermediates.
COUPLER XLV a-Benzoyl-a- (3 -octzrdecylcarbamyl ph enyl thio) -3,5 dicarboxyacetanilide To a mixture of 7 g. of Intermediate A below in 100 ml. of dioxane at 50 C. was added a solution of 3-octadecylcarbarnylphenylsulfenyl chloride (Intermediate G of coupler XXXIX above, prepared from 8.1 g. of disulfide), in 100 ml. of dioxane. This mixture was stirred for 12 hours after which time the solution was concentrated in vacuo. A solution of the gummy residue in 100 ml. of ethyl alcohol and 13 ml. of 2 N aqueous sodium hydroxide was heated at 40 C. for 1 hour after which time it was acidified with concentrated hydrochloric acid. The solid which separated was collected and recrystallized twice from ethyl alcohol, yielding 2 g. of product, M.P. l40142 C.
COUPLER XLV, INTERMEDIATE A a-Benzyl-3,5-dicarbomethoxyacetanilide To a refluxing mixture of 102 g. of ethyl a-benzoylacetate and g. of sodium acetate in 100 ml. of xylene was added 105 g. of dimethyl S-aminoisophthalate. The resulting solution was refluxed under a steam condenser for 3 hours after which time it was concentrated to /2 the original volume and cooled to room temperature. The solid which separated was collected and recrystallized from methyl alcohol, yielding 40 g. of product, M.P. 165167 C.
The following are representative development inhibitor releasing (DIR) coupler compounds of the invention that form or release development inhibitors when reacted with oxidized color developing agents.
1 hydroxy 4 phenylthio N [6 (2,4 di tertamylphenoxy) butyl] -2-naphthamide.
l hydroxy 4 (2 nitrophenylthio) N [6 (2,4- di-tert-amylphenoxy)butyl]-2-naphthamide. LVH.
1 hydroxy 4 (4 nitrophenylthio) N [6 (2,4 di -tert-amylphenoxy) butyl] -2-naphtha.mide. LVHI.
1 hydroxy 4 (2 aminophenylthio) N [6 (2,4- di-tert-amylphenoxy)butyl]-2-naphthamide. LDC.
1 hydroxy 4 (4 aminophenylthio) N [6 (2,4- di-tert-amylphenoxy)butyl]-2-naphthamide. LX.
1 hydroxy 4 (4 acetamidophenylthio) N [6- (2,4-di-tert-amylphenoxy)butyl]-2-naphthamide. LXI.
1 hydroxy 4 [2 (diethylcarbamyl)phenylthio] N- [6 (2,4 di tert amylphenoxy)butyl] 2 naphthamide. LXII.
1 hydroxy 4 (2 methylsulfonarnidophenylthio)- N [6 (2,4 di tert amylphenoxy)butyl] 2 naphthamide. LXHI.
1 hydroxy 4 (4 methylsulfonamidophenylthio)- N [6 (2,4 di tert amylphenoxy)butyl] 2 naphthamide. LXIV.
1 hydroxy 4 (2 benzothiazolylthio) N [6 (2,4- di-tert-amylphenoxy)butyl]-2-naphthamide. LXV.
l hydroxy 4 (1 phenyl 5 tetrazolylthio) N- [6 2,4 di tert amylphenoxy)butyl] 2 naphthamide.
LXVI. 0H
I CaHu-t 1 hydroxy 4 (2 benzothiazolylthio) N octadecyl- 3',5'-di-carboxy-2-naphthanilide.
LXVII. (])H (312E511 $0 OH CON-Q 2 (3,5 dichlorosulfonyl N octadecylbenzamidoy 5-methyl-4-(4-nitrophenylthio)phenol.
LXVIII. OH SOzCl I (31513141 I a NO O-- on? $0.01
1 hydroxy 4 (2 nitrophenylthio) N octadecyl 3',5-dicarboxy-2-naphthanilide.
a Benzoyl-a-phenylthio-4-[N-('y-phenylpropyD-N-(ptolyl) sulfarnyl1acetanilide.
LXX Q0 0 one onrrsomom t l a Benzoyl 0c (4-nitrophenylthio)-4[N-('y-phenyl- I propyl)-N-(p-tolyl)sulfamyl1acetanilide. 'LXXI.
a Benzoyl u-[3-(butylcarbamyl)phenylthio1-4-[N- (v-phenylpropyl N p-tolyl sulfamyl] acetanilide. LXXII.
oz Benzoyl oz [3-(butylcarbamyl) phenylthio1-4-[N- benzoyl}-a-phenylthio-2-methoxyacetanilide.
LXXIII.
C O (IJHC ONI-I C2115 S I O t-CsHn 0 CH0 ONH I I CH:
a [3-(butylcarbamyl)phenylthio]-a{3-[a-(ZA-di-tcrtamylphenoxy)butyramido]benzoyl} 2 methoxyacetanilide. LXXIV.
The above coupler (LXXVI) is suitable for use in alkaline color developing solutions in which case the sensitive element used can contain the non-diffusing coupler (DDR) providing the diffusible dye in the spontaneously developable emulsion layer overcoated with the negative or light-sensitive silver halide emulsion layer. During development coupler LXXVI forms a non-diffusible dye in the region of negative development and the mercaptotetrazole compound splits 01f and inhibits development of the underlying emulsion in the negative region, the emulsion in the positive region develops and a diffusable dye is formed from the more reactive image forming coupler which dye transfers to the reception layer thus forming a transferred positive dye image.
1 [4 A4 t butylphenoxy)phenyl]3-[a-(4-t-butylphenoxy)propionamido]4-[3-(S-mercapto-l-tetrazoly1)- phenylazo1-5-pyrazolone.
1 phenyl 3 {3-[a-(2,4-di-tert-amylphenoxy)acetamido] benzamido}4-phenylthio5-pyrazolone.
I NBC 0 CH: O
LXXV.
In other 5-pyrazolone compounds having the SR group in the 4-position, R can be any of the moieties given immediately above such as 2-nitrophenyl, aminophenyl, acylamidophenyl, etc.
1 hydroxy 4 (l-phenyl-S-tetrazolythio)N-ethyl-Z naphthamide.
LXXVI. OH
CONHOzH;
LXXIX.
1 hydroxy 4-(l-phenyl-S-tetrazolylthio)-2'-tetradecycloXy-2-naphthanilide.
1 [4- (4-tert-butylphenoxy) phenyl] 3- a- (4 tert-buty1- phenoxy propionamido]-4-( l-phenyl-S-tetrazolylthio 5- pyrazolone.

Claims (1)

1. A COLOR PHOTOGRAPHIC DIFFUSION TRANSFER PROCESS FOR TREATING AN EXPOSED PHOTOGRAPHIC ELEMENT CONTAINING LATENT NEGATIVE IMAGE REGIONS AND HAVING AT LEAST TWO COLORFORMING UNITS IN LAYERS SENSITIVE TO DIFFERENT REGIONS OF THE VISIBLE SPECTRUM, AND A BARRIER LAYER SEPARATING EACH OF SAID COLOR-FORMING UNITS COMPRISING A HYDROPHILIC COLLOID CONTAINING A WATER-INSOLUBLE REACTANT CAPABLE OF FORMING A WATER-INSOLUBLE SALT OF MERCAPTANS; EACH OF SAID COLOR-FORMING UNITS COMPRISING (1) A LIGHT-SENSITIVE EMULSION OF A HYDROPHILIC COLLOID AND A SILVERHALIDE, (2) A DEVELOPABLE EMULSION OF A HYDROPHILIC COLLOID AND A WATER-INSOLUBLE METAL SALT DEVELOPABLE TO SUBSTANTIAL DENSITY WITHOUT EXPOSURE TO LIGHT WITH A COLOR DEVELOPING AGENT, AND (3) A NONDIFFUSIBLE ACID DYE-RELEASING COUPLER CONTIGUOUS TO SAID WATER-INSOLUBLE METAL SALT OF SAID DEVELOPABLE EMULSION THAT RELEASES A DIFFUSABLE ACID DYE ON REACTION WITH AN OXIDIZED COLOR DEVELOPING AGENT; WHICH COMPRISES TREATING SAID EXPOSED PHOTOGRAPHIC ELEMENT WITH A PHOTOGRAPHIC ALKALINE COLOR DEVELOPING SOLUTION CONTAINING AN AROMATIC PRIMARY AMINO DEVELOPING AGENT SO THAT IN SAID COLOR-FORMING UNITS SAID SENSITIVE EMULSION IS DEVELOPED WITH SAID DEVELOPING AGENT IN THE PRESENCE OF A DEVELOPMENT INHIBITOR-RELEASING COUPLER THAT REACTS WITH OXIDIZED COLOR DEVELOPING AGENT TO FORM A DIFFUSIBLE MERCAPTAN DEVELOPMENT INHIBITOR IN SAID NEGATIVE IMAGE REGIONS, REACTING SAID DEVELOPMENT INHIBITOR-RELEASING COUPLER WITH RESULTING OXIDIZED DEVELOPING AGENT AND FORMING A DIFFUSIBLE MERCAPTAN DEVELOPMENT INHIBITOR, SAID DIFFUSIBLE MERCAPTAN DEVELOPMENT INHIBITOR THEREAFTER DIFFUSING TO SAID DEVELOPABLE EMULSION AN INHIBITING DEVELOPMENT IN REGIONS CORRESPONDING TO SAID NEGATIVE IMAGE REGIONS, SAID BARRIER LAYER PREVENTING SAID DIFFUSIBLE MERCAPTAN DEVELOPMENT INHIBITOR FORMED IN ONE COLOR-FORMING UNIT FROM DIFFUSING TO ANOTHER COLOR-FORMING UNIT BY FORMING AN INSOLUBLE SALT WITH MERCAPTANS DIFFUSING TO SAID BARRIER LAYER, SAID DEVELOPABLE EMULSION THEREAFTER BEING DEVELOPED WITH SAID DEVELOPING AGENT IN THE PRESENCE OF SAID ACID DYE-RELEASING COUPLER THAT REACTS WITH RESULTING OXIDIZED DEVELOPING AGENT TO FORM A DIFFUSIBLE ACID DYE IN REGIONS NOT INHIBITED AGAINST DEVELOPMENT BY SAID MERCAPTAN DEVELOPMENT INHIBITOR, AND SAID DIFFUSIBLE ACID DYE DIFFUSING IMAGEWISE IN REGISTER TO A JUXTAPOSED RECEPTION LAYER CONTAINING A MORDANT FOR ACID DYES.
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DE1199129B (en) 1965-08-19
DE1422860A1 (en) 1968-10-24
FR1339555A (en) 1963-10-11
US3701783A (en) 1972-10-31
BE591444A (en)
BE619301A (en)
GB953454A (en) 1964-03-25
BE589419A (en)
US3227554A (en) 1966-01-04
FR78161E (en) 1962-06-15
DE1422836B1 (en) 1970-04-30
DE1422839A1 (en) 1968-12-12
FR1257887A (en) 1961-04-07
GB1014725A (en) 1965-12-31
BE619300A (en)
FR1335025A (en) 1963-08-16

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