US3342599A - Schiff base developing agent precursors - Google Patents

Schiff base developing agent precursors Download PDF

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US3342599A
US3342599A US461698A US46169865A US3342599A US 3342599 A US3342599 A US 3342599A US 461698 A US461698 A US 461698A US 46169865 A US46169865 A US 46169865A US 3342599 A US3342599 A US 3342599A
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developing agent
silver halide
precursor
developing
color
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Richard L Reeves
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US461698A priority patent/US3342599A/en
Priority to BE681873D priority patent/BE681873A/xx
Priority to FR63650A priority patent/FR1481669A/fr
Priority to GB124825/66A priority patent/GB1138762A/en
Priority to DE19661547700 priority patent/DE1547700A1/de
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C5/3021—Developers with oxydisable hydroxyl or amine groups linked to an aromatic ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/32—Development processes or agents therefor
    • G03C8/36—Developers

Definitions

  • This invention relates to photographic compositions in which developing agents are incorporated in an inert precursor form.
  • this invention relates to new storage-stable, alkaline-activatable, developing agent precursors for use with such products.
  • Photographic developing agents are active reducing chemicals and generally suffer from instability when used in aqueous processing baths or when incorporated into photographic layers which must have a reasonable storage life. However, it is often desirable to incorporate them alone or with other processing addenda, in the photosensitive material and it is important to be able to do so without modifying the sensitometric characteristics adversely.
  • One object of my invention is to provide new and improved developing agent precursors which can be incorporated in stable form in photographic materials and can be rapidly cleaved by alkaline treatment to yield active developing agents.
  • Another object of my invention is to provide new and improved color-developing agent precursors which can be incorporated in stable form in photographic layers and can be rapidly cleaved by alkaline-treatment to yield active color-developing agents.
  • a further object is to provide new and improved developing agent precursors which are photographically compatible when incorporated into a silver halide emulsion or adjacent layers.
  • Another object is to provide new and improved developing agent precursors (including color-developing agent precursors) which are more rapidly soluble in aqueous liquids than the parent developing agent.
  • a further object of my invention is to provide new and improved developing agent precursors which have a high resistance to oxidation in solution or in photographic layers, and which resist hydrolysis in aqueous medium at moderate pHs up to about pH 9, but hydrolyze very rapidly to yield active developing agents at higher pHs.
  • a still further object is to provide color photographic layers which can be color developed by immersing in an alkaline activator solution.
  • Another object is to provide such developing agent precursors having ballast groups which decrease the diffusibility of the precursor compound.
  • Still another object is to provide developing agents in a precursor form showing reduced allergenic and toxic propensities.
  • Still another object of my invention is to provide new and improved multilayer color photographic materials in which the emulsion layers are provided with appropriate color-developing agent precursors, of this invention, the concentration and chemical structure of the agents being selected to fit the individual requirements of the different emulsion development.
  • Still another object is to provide multilayer photographic elements containing my new and improved developing agent precursors in any or all layers of said element.
  • the objects of my invention are achieved by using as development precursors compounds prepared by reacting the primary amino functional group or groups of a silver halide developing agent with a salicylaldehyde to form Schiffs bases which resist hydrolysis at pHs below about 9, and which hydrolyze rapidly at pHs over 9 to yield active amino developing agents.
  • the developing agent precursors of my invention made by using known aromatic amine developing agents can be represented by the following general formula:
  • R represents -OH
  • R may represent alkyl having from 1 to 18 carbon atoms, and R represents hydrogen or alkyl having from 1 to 12 carbon atoms.
  • These alkyl groups may contain substituent groups such as hydroxyl, carboxyl, sulfo, alkoxy, carboalkoxy, carboaryloxy, sulfoalkoxy, sulfoaryloXy, and an amide group, e.g., acetamido, N-methylcarbamyl, methylsulfonamido, N-methylsulfamyl, sulfamyl, etc.
  • R and R may also represent the non-metallic atoms necessary to complete a 5- or 6-membered heterocyclic ring.
  • R and R may also represent the non-metallic atoms necessary to complete a 5- or 6-membered heterocyclic ring.
  • R R R and R above.
  • R R R and R each. represents hydrogen
  • alkoxy, alkyl each of these two groups may contain from 1 to 18 carbon atoms and may also contain substituent groups as defined for R and R above), and halogen.
  • R may also represent I I OH
  • R and R may also represent the non-metallic atoms necessary to form a 5- or 6-membered isocyclic or heterocyclic ring.
  • R and R may also represent the non-metallic atoms necessary to complete a 5- or 6-Inembered isocyclic or heterocyclic ring.
  • the starting compounds i.e., developing agents and salicylaldehydes used to form the precursors, may contain substituent groups to modify such characteristics as development reactivity, solubility, diffusibility, etc. They may also contain other substituents, such as, for example, ultraviolet absorbers, antistain agents, stabilizing agents, couplers, dyes, etc.
  • Color developing agent precursor compounds typical of those of this invention are illustrated, for example, by the following:
  • N ethyl-N-(B-hydroxyethyl)-4-salicylideneaminoaniline (2) N ethyl-N-(,B-sulfoethyl)-3-rnethyl-4-salicylideneaminoaniline (3) N ethyl-N-(fi-hydroxyethyl)-4- ⁇ 5-[5-(3,5-disulfobenzamido) 2 (2,4-di-t-arnylphenoxy)benzamido]salicylideneamino ⁇ aniline disodium salt CzHs C2H4OH l NaOgS- SO Na l Cs n-t (4) 4-salicylideneaminophenol (6) 'N ethyl N methyl 3 (di ,6 hydroxyethylamino) -4-(5-octylsulfonamidosalicylideneamino) aniline Cs u
  • my novel precursor compounds are located in a light-sensitive or light-insensitive layer or proportioned between two or more such layers. These compounds undergo rapid cleavage to the respective developing agent and salicylaldehyde in the presence of an alkaline solution at pHs above about pH 9. p
  • the precursor compounds are incorporated in layers separate from the photosensitive compositions; such layers include processing webs containing processing materials which are brought into contact with the exposed photographic element to effect latent image development. Special forms of webs containing these precursors also provide nuclei or other metal-precipitating agents for the formation of diffusion transfer metal images. Other forms comprise, in addition to the precursor compounds, mordants or other means for fixing diffusion transfer dye images.
  • diifusible precursors are used to advantage in dry powder or liquid compositions for the preparation of alkaline developer solutions, in which they hydrolyze rapidly to the active developer, to develop light-sensitive photographic elements.
  • Compounds 1, 2, 4 and 10 are particularly useful in solutions to color develop photographic elements which contain incorporated couplers or those utilizing developer solutions containing difiusible couplers.
  • the precursor is more soluble than the developing agent from which it was prepared, and this can be invaluable in facilitating the preparation of developer solutions from dry powder compositions, particularly when solubilizing groups are not wanted on the developer because of requirements in the formation of nondiftusible image dyes.
  • the precursor compounds of my invention are also advantageous in solid or liquid compositions for preparing photographic developing solutions which are stable to oxidation and may be stored for long periods.
  • Such compositions preferably contain no highly alkaline material, the alkali or alkaline butler being added immediately before development, thus releasing the active developing agent.
  • Developing agent precursor g 1-20 Diifusible coupler (competing or image-forming) g 0-10 Alkaline salt g 0-100 Alkali metal sulfite g 0-50 Alkali metal bromide 'g 01() Hypo g 0-20 Thickening agents g 040' Water liter 0-1
  • My developing agent precursor compounds may be used either alone or in a combination of two or more such compounds. They may also be used in combination with other developing agents such as p-phenylenediamines, p-aminophenols, hydroquinones, aminopyrazolones, aminopyrazolines, pyrazolidones, etc.
  • Color developing agents which can be used in preparing precursor compounds useful in my invention include such compounds as, for example, diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochlon'de, Z-amino-5-diethy1aminotoluene hydrochloride, 2- amin 0-5 N-ethyl-Ndaurylamino) toluene, N-ethyl-N- (/3- methanesulfonamidoethyl)-3-methyl 4-aminoaniline sulfate, N-ethyl-N-(,B-rnethanesulfonamidoethyl) 4-aminoaniline, 4-[N-ethyl-N 3 hydroxyethyl)amino] aniline, etc., the 4-aminophenols, e.g., Z-chloro; 2,6
  • Developing agents may also be used including, for example, p-phenylenediamines, o-phenylene diamines, o-aminophenols, paminophenols, o-diaminophenols, p-diaminophenols, 4-aminopyrazolones, 3-aminopyrazolines, etc.
  • my compounds When my compounds are incorporated in emulsion layers or adjacent layers, they are particularly useful in the range of from about 0.5 to about 25 moles of precursor per mole of silver halide. Concentrations beyond these limits are also useful in other circumstances depending upon the emulsion, etc.
  • nondilfusing precursors of my invention are used to advantage in photographic emulsion layers or adjacent layers.
  • Compounds 3 and 7 are particularly useful incorporated by the Fischer method, such as that as applied to dye-forming couplers described in US. Patent 2,186,849, and as applied to ultra-violet absorbers as 7 described in U.S. Patents 2,685,512; 2,719,086; 2,739,888; and 2,784,087.
  • Nonditfusing compounds 5, 6, and 9 can be incorporated in emulsion layers by (1) solvent dispersion techniques such as are described for oil soluble couplers in U.S. Patent 2,304,939, (2) or using high-boiling organic solvents as set out in U.S. Patent 2,322,027 and (3) by methods described in US. Patent 2,801,170, and U.S. Patent 2,801,171, and U.S. Patent 2,949,360, in which low-boiling or water-soluble organic solvents are used with or in place of the high-boiling solvent.
  • solvent dispersion techniques such as are described for oil soluble couplers in U.S. Patent 2,304,939
  • high-boiling organic solvents as set out in U.S. Patent 2,322,027 and (3) by methods described in US. Patent 2,801,170, and U.S. Patent 2,801,171, and U.S. Patent 2,949,360, in which low-boiling or water-soluble organic solvents are used
  • My precursors are used in the color development of photographic hydrophilic colloid-silver halide emulsion layers of the developing-out type either in the color developer solution or in the emulsion layer.
  • the emulsions may contain silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material.
  • the precursors of my invention may also be used to advantage in image-forming layers with image-forming metal salts other than silver halide, such as ZnO, ZnS, CdS, CdSe, NiS, etc., in binders such as gelatin, polyvinyl alcohol, etc.
  • image-forming metal salts other than silver halide, such as ZnO, ZnS, CdS, CdSe, NiS, etc.
  • binders such as gelatin, polyvinyl alcohol, etc.
  • Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
  • Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate.
  • the emulsions used in the photographic element of my invention can be chemically or optically sensitized. These emulsions can be coated on a wide variety of photographic emulsion supports.
  • Color photographic materials embodying these precursors typically comprise a photographic support coated in succession with a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer either with or without a Carey Lea filter layer between the blue-sensitive and green-sensitive layers.
  • the three differentially color sensitized layers may be arranged in other orders. Couplers may be incorporated in the layers and the dyes formed may be insoluble or may be diffused and mordanted or fixed in reception layers, which may be separate or may be an integral part of the light-sensitive element.
  • the reception layer comprises a hydrophilic colloid layer containing a cationic mordant, e.g., the polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk U.S. Patent 2,882,156.
  • Other mordants include the 2-vinyl pyridine polymer quaternized with methyl-p-toluene sulfonate and similar compounds.
  • the developing agent precursor compounds of my invention are prepared by stirring a warm mixture of a developing agent and a salicylaldehyde or substituted salicylaldehyde and concentrating the resulting solution until the product is precipitated.
  • a typical synthesis is described in Example 1 below.
  • the attached drawing illustrates a multilayer color photographic element.
  • a cellulose acetate opaque white film support has in order, beginning with the support, a gelatin layer 11 containing the developing agent precursor which also serves as the antihalation material. Over the precursor layer is coated a gelatino-silver bromoiodide emulsion 12 sensitized to red light, a gelatin interlayer
  • Example 1 Preparation of N-ethyl-N-(B-sulfoethyl) 3 methyl-4- salicylideneaminoaniline, Compound N0. 2.A slurry of 12.9 g.
  • Example 2 The compounds of my invention are particularly advantageous because of the rapidity with which the developing agent is released on hydrolysis of the developing agent precursor in alkaline solutions of high pH, such as pH 12; a property which is not exhibited by color developing agent precursors in the prior art.
  • Compound No. 2 of Example 1 releases the developing agent approximately 1600 times faster at pH 12 than does the prior art compound, N,N-diethyl- 3 methyl 4 (2-sulfobenzylidene amino)aniline sodium salt.
  • Example 3 A weighed sample of developing agent precursor sufficient to give a 1 10- M solution after dilution, is dissolved in 1 ml. of ethanol in a volumetric flask and thermostated at 25.0 C. This sample is diluted to ml. with aqueous phosphate or carbonate butter having an ionic strength of 0.05. The disappearance of the developing agent precursor is followed on a Beckman DU spectrophotometer at a wavelength that gives the greatest difference in absorbance between the precursor and aldehyde. The first-order rate constants are calculated by the Guggenheim method.
  • the following example illustrates the ability of the compounds of my invention to release active developing agent during the processing of a photographic element.
  • Example 4 A single layer gelatin-silver bromoiodide emulsion was coated on a conventional support.
  • the constituents per square foot of coated emulsion comprised: 7.8 parts of gelatin, 3,3 parts of silver, 1 part of the coupler, l-phenyl- 3-(3,5-disulfobenzamido) 4 (2-hydroxy-4-pentadecylphenylazo-)-5-pyrazolone dipotassium salt, and 1.7 parts of Compound No. 3 as the developing agent precursor.
  • a second single layer control coating was prepared that was similar in all respects to the first coating except that a non-salicylidene developing agent precursor was used: N-ethyl-N- (B-hydroxyethyl)-4- ⁇ 5-[S-(3,5-disulfobenzamido)-2-(2,4 di t amylphenoxy)benzamido] benzylidene ⁇ aniline.
  • the exposed film strips were dipped for 35 seconds in an activator solution having the following composition:
  • Example 5 A storage-stable processing web was prepared by applying a gelatin coating containing 5 parts by weight of gelatin and 1 part by weight of Compound No. 3 (suflicient to yield enough active developing agent to completely develop the multilayer color film described below) onto a subbed cellulose acetate support.
  • Example 6 A multilayer color film similar to that described in Example 5 was prepared except that it was coated over a gelatin layer (i.e., which had been coated on a clear cellulose acetate film support) which contained a sufiicient amount of precursor Compound No. 10 to yield enough active developing agent to completely develop the color film.
  • a gelatin layer i.e., which had been coated on a clear cellulose acetate film support
  • a sufiicient amount of precursor Compound No. 10 to yield enough active developing agent to completely develop the color film.
  • the processed film contained a good quality negative color reproduction of the subject.
  • the practice of my invention comprises the use of N-salicylidene derivatives of developing agents containing at least one amino group as inert precursors of the developing agents. These derivatives cleave readily under alkaline conditions to yield the active form of developing agent.
  • composition of the moiety to which the amino group is attached has no effect on the inertness of the precursor compounds of my invention and their rapid decomposition under alkaline conditions, it will be understood that changes in the character and degree of substitution of said moiety can be made to satisfy specific requirements of reactivity, solubility, and diffusibility imposed when my compounds are incorporated in photographic compositions.
  • My novel compounds are used to advantage in developing photographic film (i.e., either black-and-white or color film) containing magenta couplers, e.g., pyrazolones,
  • cyanoacetylcoumarones indazolones, etc.
  • yellow couplers e.g., a-acylacetanilides, dibenzoylmethanes, etc.
  • cyan couplers e.g., naphthols, phenols, etc., which couplers can form either diffusible or n-onditfusible image dyes.
  • a dry silver halide developing composition adapted to be mixed with water for developing a latent image in a silver halide emulsion the improvement comprising, as a developing agent precursor, a Schiif base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylideneamino group and having the property of hydrolyzing rapidly in alkaline medium at a pH above 9 to release a primary amino silver halide developing agent.
  • a Schiif base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylideneamino group and having the property of hydrolyzing rapidly in alkaline medium at a pH above 9 to release a primary amino silver halide developing agent.
  • an aqueous silver halide developing concenerate comprising, as a developing agent precursor, a Schiff base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylideneamino group and having the property of hydrolyzing rapidly in alkaline medium at a pH above 9 to release a primary amino silver halide developing agent.
  • a Schiif base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylideneamino group and having the property of hydroylzing rapidly in alkaline medium at a pH above 9 to release a primary amino silver halide developing agent.
  • a photographic element comprising a support having thereon a light-sensitive unexposed silver halide emulsion containing therein, as a developing agent precursor, a Schifi. base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylideneamino group and having the property of hydrolyzing rapidly in alkaline medium at a pH above 9 to release a primary amino silver halide developing agent.
  • a light-sensitive photographic element comprising a support having thereon a coating containing, as a developing agent precursor, a Schiif base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylidene amino group and having the property of hydrolyzing rapidly in alkaline medium at a pH above 9 to release a primary amino silver halide developing agent.
  • a Schiif base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylidene amino group and having the property of hydrolyzing rapidly in alkaline medium at a pH above 9 to release a primary amino silver halide developing agent.
  • a photographic element comprising a support having thereon an unexposed light-sensitive silver halide emulsion containing N ethyl N-(B-hydroxyethyl)-4- salicylideneaminoaniline.
  • a photographic element comprising a. support having thereon an unexposed light-sensitive silver halide emulsion containing N-ethyl-N-(fl-sulfoethyl)-3-methy1-4- salicylideneaminoaniline.
  • a photographic element comprising a support having thereon an unexposed light-sensitive silver halide emulsion containing N-ethyl-N- (fl-hydroxyethyl)-4- ⁇ 5-[5- (3,5 disulfobenzamid-o) 2(2,4-di-t-amylpi1enoxy) benzamido]salicylideneamino ⁇ aniline disodium salt.
  • a photographic element comprising a support having thereon an unexposed light-sensitive silver halide emulsion containing 4-salicylideneaminophenol.
  • a photographic element comprising a support having thereon an unexposed light-sensitive silver halide emulsion containing N-ethyl-N-(B-methylsulfonamidothyl) 4 ⁇ 4-[a-(3 pen-tadecylphenoxy)acetamindo] salicylideneamino ⁇ aniline.
  • a photographic element comprising a support having thereon an unexposed light-sensitive silver halide emulsion layer containing at least one color former which reacts with the oxidation product of a primary aromatic amine color developer and having asa developing agent precursor, a Schiff base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylideneamino group and having the property of hydrolyzing rapidly at a pH above 9 to release a primary amino siliver halide color development agent.
  • a light-insensitive photographic element comprising a support having thereon a coating containing silver halide precipitating nuclei and, as a developing agent precursor, a Schiif base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylideneamino group and having the property of hydrolyzing rapidly in alkaline medium at a pH above 9 to release a primary amino silver halide developing agent.
  • a rnulti-layer photographic element comprising a support having thereon at least one layer containing an unexposed light-sensitive silver halide emulsion containing at least one color coupler which reacts with the oxidation product of a primary aromatic amine color developer to form a dye and containing in at least one layer, as a developing agent precursor, a Schiff base which is a condensate of a salicylaldehyde with a silver halide developing agent, said condensate having at least one salicylaldehyde amino group and having the property of hydrolyzing rapidly at a pH above 9 to release said primary amino silver halide color developing agent.
  • a multi-layer photographic element comprising a support with thereon at least one unexposed photographic silver halide emulsion layer sensitive to the blue region of the spectrum, at least one layer spectrally sensitized to the green region of the spectrum, and at least .one unexposed photographic silver halide emulsion layer spectrally sensitized to the red region of the spectrum, and containing in at least one layer of said multi-layer photographic element, as a developing agent precursor, a S-chiff base which is a condensate of a salicyladehyde with a silver halide developing agent, said condensate having at least one salicylideneamino group and having the property of hydrolyzing rapidly in alkaline medium at a pH above 9 to release a primary amino silver halide color development agent.
  • a Schiff base which is a condensate of a salicylaldehyde with a siliver halide developing agent, said condensate having at least one salicylideneamino group
  • contacting said emulsion with an alkaline agent to raise the pH of said emulsion to above 9 and to release said silver halide developing agent from said precursor.

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US461698A 1965-06-07 1965-06-07 Schiff base developing agent precursors Expired - Lifetime US3342599A (en)

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Application Number Priority Date Filing Date Title
US342599D USB342599I5 (xx) 1965-06-07
US461698A US3342599A (en) 1965-06-07 1965-06-07 Schiff base developing agent precursors
BE681873D BE681873A (xx) 1965-06-07 1966-05-31
FR63650A FR1481669A (fr) 1965-06-07 1966-06-01 Nouveaux composés précurseurs de développateurs et produits photographiques contenant ces composés
GB124825/66A GB1138762A (en) 1965-06-07 1966-06-03 Photographic silver halide development
DE19661547700 DE1547700A1 (de) 1965-06-07 1966-06-03 Verwendung von Schiff'schen Basen zur Entwicklung von belichtetem,photographischem Material

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Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4157915A (en) * 1977-05-02 1979-06-12 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material containing development precursor
US4232113A (en) * 1979-03-14 1980-11-04 Minnesota Mining And Manufacturing Company Liquid concentrated developer composition, and confection ready to mix with water including it, for use in color photography
US4297437A (en) * 1979-11-22 1981-10-27 Konishiroku Photo Industry Co., Ltd. Processing method of silver halide color photographic material
EP0047449A2 (de) * 1980-09-09 1982-03-17 Agfa-Gevaert AG Verfahren zur Herstellung farbfotografischer Bilder
EP0050260A1 (de) * 1980-10-16 1982-04-28 Agfa-Gevaert AG Fotografisches Material, Herstellungsverfahren sowie Verfahren zur Herstellung fotografischer Bilder
US4390617A (en) * 1980-03-18 1983-06-28 Konishiroku Photo Industry Co., Ltd. Method for the formation of photographic images
US4430424A (en) 1981-09-04 1984-02-07 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material
EP0143570A2 (en) 1983-11-02 1985-06-05 Konica Corporation Silver halide color photographic material
EP0219113A2 (en) 1985-10-15 1987-04-22 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic material
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
EP0313083A2 (en) 1987-10-22 1989-04-26 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0317983A2 (en) 1987-11-27 1989-05-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0318987A1 (en) 1987-12-02 1989-06-07 Fuji Photo Film Co., Ltd. Direct positive photographic lightsensitive material
EP0320939A2 (en) 1987-12-15 1989-06-21 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0435334A2 (en) 1989-12-29 1991-07-03 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing yellow colored cyan coupler
EP0440195A2 (en) 1990-01-31 1991-08-07 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0456210A2 (en) 1990-05-09 1991-11-13 Fuji Photo Film Co., Ltd. Method for processing a silver halide photographic material and light-sensitive material for photographing
EP0459210A1 (en) * 1990-05-14 1991-12-04 Fuji Photo Film Co., Ltd. Color developing agent and process for forming image
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563985A1 (en) 1992-04-03 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5292611A (en) * 1991-12-17 1994-03-08 Konica Corporation Dye image forming method
US5302498A (en) * 1991-12-19 1994-04-12 Eastman Kodak Company Element and process for photographic developer replenishment
EP0607905A2 (en) 1993-01-18 1994-07-27 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5411840A (en) * 1992-12-21 1995-05-02 Eastman Kodak Company Low volume processing for establishing boundary conditions to control developer diffusion in color photographic elements
EP0724194A1 (en) 1995-01-30 1996-07-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5547810A (en) * 1994-09-16 1996-08-20 Konica Corporation Image forming method with alkali precursor
US6261757B1 (en) 2000-06-13 2001-07-17 Eastman Kodak Company Photographic element comprising an ion exchanged reducing agent
US6306551B1 (en) 1999-12-30 2001-10-23 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6312879B1 (en) 1999-12-30 2001-11-06 Eastman Kodak Company Photographic or photothermographic element containing a blocked photographically useful compound
US6316173B1 (en) 2000-06-13 2001-11-13 Eastman Kodak Company Sheet comprising an ion exchanges reducing agent and methods of processing photographic elements in the presence of said sheet
US6319640B1 (en) 2000-05-26 2001-11-20 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6379876B1 (en) 2000-06-13 2002-04-30 Eastman Kodak Company Thermally processable imaging element comprising an ion exchanged reducing agent
US6413708B1 (en) 2000-05-26 2002-07-02 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6426179B1 (en) 1999-12-30 2002-07-30 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6440618B1 (en) 2000-05-26 2002-08-27 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6455235B1 (en) * 1999-12-17 2002-09-24 Konica Corporation Photographic processing element and image forming method by the use thereof
US6506546B1 (en) 1999-12-30 2003-01-14 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6537712B1 (en) 2000-06-13 2003-03-25 Eastman Kodak Company Color photothermographic elements comprising blocked developing agents
US6749977B1 (en) 2003-01-09 2004-06-15 Eastman Kodak Company Imaging element containing a polymeric heteroaromatic blocked developer
US6756192B1 (en) 1999-12-30 2004-06-29 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6770406B1 (en) 2003-01-09 2004-08-03 Eastman Kodak Company Imaging element containing a polymeric benzylic blocked developer

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US2507114A (en) * 1946-08-21 1950-05-09 Du Pont Aryl azo methine sulfonic acids
US2695234A (en) * 1951-01-26 1954-11-23 Gevaert Photo Prod Nv Photographic development
US3132140A (en) * 1961-05-10 1964-05-05 Du Pont Schiff bases and metal chelate pigments made therefrom

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US2507114A (en) * 1946-08-21 1950-05-09 Du Pont Aryl azo methine sulfonic acids
US2695234A (en) * 1951-01-26 1954-11-23 Gevaert Photo Prod Nv Photographic development
US3132140A (en) * 1961-05-10 1964-05-05 Du Pont Schiff bases and metal chelate pigments made therefrom

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4157915A (en) * 1977-05-02 1979-06-12 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material containing development precursor
US4232113A (en) * 1979-03-14 1980-11-04 Minnesota Mining And Manufacturing Company Liquid concentrated developer composition, and confection ready to mix with water including it, for use in color photography
US4297437A (en) * 1979-11-22 1981-10-27 Konishiroku Photo Industry Co., Ltd. Processing method of silver halide color photographic material
US4390617A (en) * 1980-03-18 1983-06-28 Konishiroku Photo Industry Co., Ltd. Method for the formation of photographic images
EP0047449A2 (de) * 1980-09-09 1982-03-17 Agfa-Gevaert AG Verfahren zur Herstellung farbfotografischer Bilder
EP0047449A3 (en) * 1980-09-09 1983-03-16 Agfa-Gevaert Aktiengesellschaft Process for the production of colour-photographic images
US4386155A (en) * 1980-09-09 1983-05-31 Agfa-Gevaert Ag Process for the production of photographic images
EP0050260A1 (de) * 1980-10-16 1982-04-28 Agfa-Gevaert AG Fotografisches Material, Herstellungsverfahren sowie Verfahren zur Herstellung fotografischer Bilder
US4358531A (en) * 1980-10-16 1982-11-09 Agfa-Gevaert Aktiengesellschaft Photographic material, process for the production thereof and process for the production of photographic images
US4430424A (en) 1981-09-04 1984-02-07 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material
EP0143570A2 (en) 1983-11-02 1985-06-05 Konica Corporation Silver halide color photographic material
EP0219113A2 (en) 1985-10-15 1987-04-22 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic material
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
EP0313083A2 (en) 1987-10-22 1989-04-26 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0317983A2 (en) 1987-11-27 1989-05-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0318987A1 (en) 1987-12-02 1989-06-07 Fuji Photo Film Co., Ltd. Direct positive photographic lightsensitive material
EP0320939A2 (en) 1987-12-15 1989-06-21 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0435334A2 (en) 1989-12-29 1991-07-03 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing yellow colored cyan coupler
EP0440195A2 (en) 1990-01-31 1991-08-07 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0456210A2 (en) 1990-05-09 1991-11-13 Fuji Photo Film Co., Ltd. Method for processing a silver halide photographic material and light-sensitive material for photographing
EP0459210A1 (en) * 1990-05-14 1991-12-04 Fuji Photo Film Co., Ltd. Color developing agent and process for forming image
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
US5292611A (en) * 1991-12-17 1994-03-08 Konica Corporation Dye image forming method
US5302498A (en) * 1991-12-19 1994-04-12 Eastman Kodak Company Element and process for photographic developer replenishment
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563985A1 (en) 1992-04-03 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5411840A (en) * 1992-12-21 1995-05-02 Eastman Kodak Company Low volume processing for establishing boundary conditions to control developer diffusion in color photographic elements
EP0607905A2 (en) 1993-01-18 1994-07-27 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5547810A (en) * 1994-09-16 1996-08-20 Konica Corporation Image forming method with alkali precursor
EP0724194A1 (en) 1995-01-30 1996-07-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US6455235B1 (en) * 1999-12-17 2002-09-24 Konica Corporation Photographic processing element and image forming method by the use thereof
US6426179B1 (en) 1999-12-30 2002-07-30 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6756192B1 (en) 1999-12-30 2004-06-29 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6306551B1 (en) 1999-12-30 2001-10-23 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6312879B1 (en) 1999-12-30 2001-11-06 Eastman Kodak Company Photographic or photothermographic element containing a blocked photographically useful compound
US6759187B1 (en) 1999-12-30 2004-07-06 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6506546B1 (en) 1999-12-30 2003-01-14 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US7414146B2 (en) 2000-05-26 2008-08-19 Carestream Health, Inc. Imaging element containing a blocked photographically useful compound
US6440618B1 (en) 2000-05-26 2002-08-27 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6413708B1 (en) 2000-05-26 2002-07-02 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US6319640B1 (en) 2000-05-26 2001-11-20 Eastman Kodak Company Imaging element containing a blocked photographically useful compound
US20030129552A1 (en) * 2000-05-26 2003-07-10 Slusarek Wojciech K. Imaging element containing a blocked photographically useful compound
US6379876B1 (en) 2000-06-13 2002-04-30 Eastman Kodak Company Thermally processable imaging element comprising an ion exchanged reducing agent
US6537712B1 (en) 2000-06-13 2003-03-25 Eastman Kodak Company Color photothermographic elements comprising blocked developing agents
US6316173B1 (en) 2000-06-13 2001-11-13 Eastman Kodak Company Sheet comprising an ion exchanges reducing agent and methods of processing photographic elements in the presence of said sheet
US6261757B1 (en) 2000-06-13 2001-07-17 Eastman Kodak Company Photographic element comprising an ion exchanged reducing agent
US6749977B1 (en) 2003-01-09 2004-06-15 Eastman Kodak Company Imaging element containing a polymeric heteroaromatic blocked developer
US6770406B1 (en) 2003-01-09 2004-08-03 Eastman Kodak Company Imaging element containing a polymeric benzylic blocked developer

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GB1138762A (en) 1969-01-01
DE1547700A1 (de) 1970-03-26
BE681873A (xx) 1966-10-31
USB342599I5 (xx)

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