US3419390A - Elements and developers for color photography utilizing phenolic couplers containingan aminoalkyl group on the coupling position - Google Patents

Elements and developers for color photography utilizing phenolic couplers containingan aminoalkyl group on the coupling position Download PDF

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US3419390A
US3419390A US492904A US49290465A US3419390A US 3419390 A US3419390 A US 3419390A US 492904 A US492904 A US 492904A US 49290465 A US49290465 A US 49290465A US 3419390 A US3419390 A US 3419390A
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couplers
coupler
group
color
dye
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Homer W J Cressman
John R Thirtle
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Eastman Kodak Co
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen 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
    • C07D215/38—Nitrogen atoms
    • 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
    • G03C7/18—Processes for the correction of the colour image in subtractive colour photography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30523—Phenols or naphtols couplers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors

Definitions

  • This invention relates to color photography and more particularly to new and improved cyan dye-forming coupler compounds for the formation of images.
  • the color-forming coupler may be either in the developer solution or incorporated in the light-sensitive photographic emulsion layer so that, during development, it is available in the emulsion layer to react with the color developing agent that is oxidized by silver image development.
  • Diiiusible couplers are used in color developer solutions.
  • Nondifi'using couplers are incorporated in photographic emulsion layers.
  • Another object is to provide new aminoalkyl substituted four-equivalent couplers 'which have good coupling reactivity and which include the diffusible type coupler, the Fischer-type and the nondiifusing type couplers which are readily incorporated in light-sensitive hydrophilic colloidsilver halide emulsion layers by means of a wide range of coupler-to-solvent ratios.
  • Still another object of our invention is to provide new uncolored cyan-dye-forming couplers which aiford automatic color correction for the cyan dye image.
  • Another object is to provide new image-forming layers containing our new couplers alone or in a hydrophilic colloid such that the coupler is contiguous to light-sensitive silver halide, ZnO, ZnS, CdS, CdSe, NiS, etc., either with or without a binder.
  • Still another object is to provide improved cyan dye photographic images and improved multicolor photographic images by the use of these new couplers.
  • Another object is to provide new dilr'usible cyan imageforming couplers for use in cyan color developer solutions.
  • Our new cyan-dye-forming couplers are derived from any of the known phenolic or naphtholic cyan-forming four-equivalent couplers by substituting an aminoalkyl group on the carbon atom in the coupling position of the coupler, the said amino group having at least one hydrogen atom.
  • R group in the above formula represents an alkoxy group, either straight or branched chain, particularly those of from 1 to 22 carbon atoms (e.g., ethoxy, isopropoxy, decyloxy, octadecyloxy, docosoxy, etc.), a mono or bicyclic alkoxy group such as cyclohexyloxy, cyclopentoxy, norbornyloxy, etc.
  • the alkoxy group may contain substituent groups such as halogen, nitro, hydroxyl, carboxyl, amino, carboxyl ester, e.g., carbomethoxy, sulfo, sulfo esters, e.g., methoxysulfonyl, alkoxy as hereinabove defined, amide, etc. such that when the R group is a carboxyl or sulfo substituted alkoxy group, the coupler contains sufiicient ballasting to render a dye from said coupler nondiifusing.
  • substituent groups such as halogen, nitro, hydroxyl, carboxyl, amino, carboxyl ester, e.g., carbomethoxy, sulfo, sulfo esters, e.g., methoxysulfonyl, alkoxy as hereinabove defined, amide, etc.
  • the R group may also represent an amide group such as acetamido, ethylsulfonamido, N-methylbutyramido, N-propylbenzamido, 4-t-butylbenzamido, carbarnyl, N-octadecylcarbamyl, N,N-dihexylcarbamyl, N-
  • amide groups may also be substituted with groups such as defined for the substituted alkoxy group in R above (e.g., halogen, nitro, hydroxyl, carboxyl, amino, carboxyl esters, sulfo esters, amide, etc.).
  • the R group represents a hydrogen atom, an alkyl group, either straight or branched chain of from 1 to 22 carbon atoms (e.g., methyl, ethyl, isopropyl, tertiary butyl, dodecyl, docosyl, etc.), a mono or bicyclic alkyl group such cyclopentyl, norbornyl, etc., or an aryl group such as phenyl, napthyl, etc.
  • These groups, i.e., alkyl and aryl may also be substituted with groups such as defined for the substituted alkoxy groups in R above.
  • the R and R groups each represent the hydrogen atom, a halogen atom, an alkyl, aryl, alkoxy, or amide group as defined in R and R above.
  • the R and R groups may also represent the non-metallic atoms needed to complete a fused ring, such as a 5,6- and 6,6-1nembered isoeyclic and heterocyclic rings, e.g., naphthalene, quinoline, benzothiazole, benzimidazole, etc.
  • phenolic (i.e., phenols and naphthols) couplers are characterized by having an amino alkyl group on the coupling position of the coupler which gives them good coupling reactivity and other valuable properties. These couplers are particularly characterized by the low levels of unwanted color fog produced. Excellent coupling reac tivity is obtained with couplers of our invention when incorporated in emulsion layers without the use of highboiling coupler solvents. When high-boiling solvents are used to disperse these couplers, high dye yield and low color fog are attained over a wide range of coupler-tosolvent ratios. When the ditfusible couplers of our invention are used in color developing solutions, excellent reactivity and good dye yield are achieved.
  • Couplers of Formulas I and II are the following typical examples used to illustrate but not limit our invention.
  • the aminoalkyl group provides a means of attaching other substituents to our couplers such as, for example, preformed dyes useful in color correction, and the like. Additional ballasting groups can conveniently be introduced via the aminoalkyl group; these ballasting groups are then eliminated during the coupling reaction with oxidized color developer which forms theimage dyes.
  • the diffusible couplers of our invention are used to advantage in color developer solutions used to color develop light-sensitive elements used for color photography which do not contain the color-forming coupler.
  • Any of the well known primary aromatic amino color-forming silver halide developing agents such as the phenylenediamines, e.g., diethyl-pphenylenediamine hydrochloride, 'monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, Z-amino-S-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-lauryl)aminotoluene, N-ethyl- 7 f? methanesulfonamidoethyl 3 methyl 4 amino,
  • aniline, 4-N-ethyl-N-B-hydroxyethylaminoaniline, etc., the p-aminophenols and their substitution products where the amino group is unsubstituted may be used in the alkaline developer solution with our couplers.
  • Various other materials may be included in the developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisulfite, bromide, iodide, etc., and the thickening agents used in viscous developer compositions. The following is a typical developer solution given to illustrate but not limit our invention.
  • Couplers such as 9, 11, illustrate those that are incorporated as Fischertype couplers.
  • the other nondiifusing couplers e.g., 7, 8, 10, 12, 13, 14, 15, 16, 17 19, 21, 22, 23, are incorporated in emulsion layers by methods such as are described by Mannes et al. U.S. Patent 2,304,939, issued Dec. 15, 1942, Jelley et al., U.S. Patent 2,322,027, issued June 15, 1943, etc., in which high-boiling organic solvents ase used to dissolve the coupler, and by methods described in Vittum et al., U.S.
  • Patent 2,801,170, and Fierke et al. U.S. Patent 2,801,171, both issued July 30, 1957, and Julian, U.S. Patent 2,949,360, issued Aug. 16, 1960, in which low-boiling or water-soluble organic solvents are used with or in place of the high-boiling solvent.
  • the use of such coupler dispersions permits thinner emulsion layers. These thinner layers are very desirable because they cause less light scattering, consequently, they produce sharper images.
  • Coupler 20 contains a preformed dye attached to the coupler on the phenylaminoalkyl group. This dye is eliminated on the coupling of the coupler with an oxidized color developer and diffuses out of the film.
  • This conpler can be used as a magentacolored coupler for the purpose of correcting for the unwanted green absorption of cyan image dyes, i.e., that formed from the coupler itself as well as that formed from other cyan couplers. Generally, such a coupler as this would be used in combination with another image-forming cyan coupler in the same layer.
  • the couplers are used to advantage in the color de velopment of photographic image-forming layers of the developing-out types.
  • the light-sensitive materials used to advantage in our image-forming layers include silver halide (e.g., silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc.), ZnO, ZnS, CdS, CdSe, NiS, etc., either with or without a hydrophilic colloid binder.
  • our couplers are contiguous with the said light-sensitive material either in the same layer or in a contiguous layer.
  • Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
  • Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in U.S. Patent 2,286,215, a far-hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 1926%, as described in U.S. Patent 2,327,808, a water-soluble ethanolamine cellulose acetate as described in U.S.
  • Patent 2,322,085 a polyacrylamide having a combined acrylamide content of -60% and a specific viscosity of 0.25l.5 or an imidized polyacrylamide of like acrylamide content and viscosity as described in U.S. Patent 2,541,474, zein as described in U.S. Patent 2,563,791, a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in U.S. Patent 2,768,154, or containing cyano-acetyl groups, such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in U.S. Patent 2,808,331, or a polymeric material which results from polymerizing a protein or a saturated acrylated protein with a monomer having a vinyl group as described in U.S. Patent 2,852,382.
  • the silver halide or other lightsensitive material used in the photographic element of our invention can be chemically sensitized or optically sensitized by any of the accepted procedures.
  • our emulsion are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support.
  • the support is coated in succession with a redsensitive layer, a green-sensitive layer, and a blue-sensitive layer eirther with or without a Carey Lea filter between the blue-sensitive and green-sensitive layers.
  • the three differently color-sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer.
  • these light-sensitive layers are arranged on the same side of the support.
  • EXAMPLE 1 The ability of the phenolic coupling agents of our invention to undergo chromogenic development with oxidized developing agent depends on the elimination of the aminoalkyl group located in the coupling position of the coupling agent. The ease of displacement for two of the couplers of our invention was measured by determining the coupling rate relative to phenol. The results are recorded in Table I. The procedure was that of Tong and Glesmann, J.A.C.S., 79, 583 (1957), using a jet-mixing machine described by W. R. Ruby, Rev. Sci. Instruments, 26, 460 (1955).
  • EXAMPLE 2 A single layer gelatin silver bromoiodide emulsion containing coupler 7 and coupler solvent di-n-butylphthalate was made. This coating contained 10 parts of gelatin, 5 parts of silver, 2 parts of coupler, and 1 part of coupler solvent. A strip of the above mentioned coating was given -second exposure on a 1B intensity scale sensitometer and processed in a conventional manner to a color negative using the following developer solution.
  • the image dye which was formed in the processed strip had a x of 690 m and a l) of 2.4.
  • This processed strip was then immersed in a ferricyanide bleach bath, and the residual coupler formed a yellow dye image (i.e., positive image) which affords automatic color correction by providing a color-correcting mask for the unwanted blue absorption of the cyan dye image.
  • This yellow mask image had a )t of 477 my. and :a D of 0.4.
  • couplers of our invention are used to advantage in color photography as illustrated previously with representative couplers.
  • the couplers of our invention are valuable as cyan image-forming couplers in multilayer photographic color films containing other classes of couplers in the other layers of said film.
  • Such other couplers are, for example, magenta-forming pyrazolones, cyanoacetyl coumarones, indazolones, etc., and yellow couplers such as a-acylacetanilides and dibenzoylmethanes.
  • Couplers 4, 5 and 7 through 23 are prepared by a basic synthesis involving the following steps:
  • step (1) (2) tReacting the product of step (1) with an amine to form a Schiff base;
  • step (3) Reducing the Schiif base formed in step (2) to a phenol having an aminomcthyl group in the 4-position.
  • the four-equivalent image-forming couplers of our invention are distinguished from other four-equivalent couplers by having an aminoalkyl group substituted on the coupling position of the coupler molecule.
  • Our couplers are characterized by not producing color fog, and by having very good coupling reactivity.
  • the couplers of our invention may be used in emulsion layers either alone or admixed with other couplers, either four-equivalent couplers, competing couplers, and the like.
  • An image-forming layer containing silver halide and contiguous thereto a coupler which is capable of forming a cyan dye on coupling with the oxidation product of a primary aromatic amino color developing agent, said coupler containing at least one phenolic coupling moiety, said phenolic coupling moiety being substituted in the coupling position with an aminomethyl group, said amino group having at least one hydrogen atom, and said phenolic coupling moiety being substituted in a position ortho to the hydroxyl group with a group selected from the class consisting of an alkoxy group and an amide group, said dye being nondiffusing.
  • R represents a group selected from the class consisting of an alkoxy group and an amide group
  • R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group
  • R and R each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an amide group, and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazoie, said coupler being capable of forming a nondiffusing dye.
  • R represents a group selected from the class consisting of an alkoxy group and an amide group
  • R' represents a group selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group
  • R and R each represents -a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an amide, and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazole, said coupler being capable of forming a nonditiusing dye.
  • R represents a group selected from the class consisting of an alkoXy group and an amide group
  • R and R each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an amide group, and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazole, said coupler being capable of forming a nondittusing dye.
  • a cyan color developer comprising an aqueous alkaline solution containing a primary aromatic amino color developing agent and a ditfusi'ble coupler selected from those having the formulas:
  • R represents a group selected from the class consisting of an alkoxy group and an amide group
  • R' represents a group selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group
  • R and R each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an amide group, and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazole, said coupler reacting with oxidized color developing agent to form a nondifiusing dye.
  • a cyan color developer comprising an aqueous alkaline solution containing a primary aromatic amino color developing agent and a diffusible coupler selected from those having the formulas:
  • R represents a group selected from the class consisting of a lower alkoxy group and the amide group
  • R represents a group selected from the class consisting of the hydrogen atom, a lower alkyl group and phenyl
  • R and R each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, phenyl and an amide group and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazole, said coupler reacting with oxidized color developing agent to form a nondifiusing dye.
  • a cyan color developer comprising an aqueous alkaline solution containing a primary aromatic amino color developing agent and a ditiusible coupler selected from the class consisting of 4-aminomethyl-2-methoxyphenol, 4-butylaminomethyl-Z-methoxyphenol, 4-anilinomethyl-Z-methoxyphenol, 1-hydroxy-4-ethylaminomethyl- 2 naphthamide, 2 ethoxy 4-propylaminomethyl-S-acetamido 1 naphthol, a,a' iminobis (4-methyl-2-methoxyphenol), and S-(N-ethylaminomethyl)-7-acetamido-8-hydroxyquinoline, said coupler reacting with oxidized color developing agent to form a nondifr'using dye.
  • a ditiusible coupler selected from the class consisting of 4-aminomethyl-2-methoxyphenol, 4-butylaminomethyl-Z-methoxyphenol, 4-anilinomethyl-Z-meth
  • R 2 H B should read I 11 -1 R EN R/R CH N and in line 37 between "amide” and insert -group- Column 1 0, lines 28 through 35, in the s cortural formula on the right -hand side of the column, that part of the structure re adin H I 1 H I I l CH2-CCH2 should read cH Ne1-1 SIGNED AND SEALED MAY 261970 (SEAL) Attest:

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Description

United States Patent ELEMENTS AND DEVELOPERS FOR COLOR PHO- TOGRAPHY UTILIZING PHENOLIC COUPLERS CONTAINING AN AMINOALKYL GROUP ON THE COUPLING POSITION Homer W. J. Cressman and John R. Thirtle, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Continuation-impart of application Ser. No. 452,932, May 3, 1965. This application Oct. 4, 1965, Ser. No. 492,904
13 Claims. (CI. 96-55) ABSTRACT OF THE DISCLOSURE Cyan dye-forming phenolic and naphtholic couplers having an aminomethyl substituent attached to the active carbon of the couplers are used to advantage in color photography to form nondiifusible cyan dye images in color photographic elements because of their high coupling reactivity and very low density of unwanted color fog that is formed by color development.
This is a continuation-in-part application of Homer W. J. Cressman and John R. Thirtle, U.S. Ser. 452,932, filed May 3, 1965, now abandoned.
This invention relates to color photography and more particularly to new and improved cyan dye-forming coupler compounds for the formation of images.
The formation of colored photographic images by the imagewise coupling of oxidized aromatic primary amino developing agents with color-forming or coupling compounds to form indophenol, indoaniline, and azomethine dyes is well known. In these processes, the subtractive process of color formation is ordinarily used and the image dyes customarily formed are cyan, magenta, and yellow, the colors that are complementary to the primary colors, red, green, and blue, respectively. Usually phenol or naphthol couplers are used to form the cyan dye image; pyrazolone or cyanoacetyl derivative couplers are used to form the magenta dye image; and acylacetamide couplers are used to form the yellow dye image.
In these color photographic systems, the color-forming coupler may be either in the developer solution or incorporated in the light-sensitive photographic emulsion layer so that, during development, it is available in the emulsion layer to react with the color developing agent that is oxidized by silver image development. Diiiusible couplers are used in color developer solutions. Nondifi'using couplers are incorporated in photographic emulsion layers.
It is an object of our invention to provide new and improved couplers capable of forming cyan dye with the oxidation product of a primary aromatic amino color developing agent.
It is a further object to provide new and improved low-fogging cyan couplers with good reactivity so that processing can be accomplished in a reasonable time and without prolonging development or without requirement for excessively high pH or high temperature processing conditions.
Another object is to provide new aminoalkyl substituted four-equivalent couplers 'which have good coupling reactivity and which include the diffusible type coupler, the Fischer-type and the nondiifusing type couplers which are readily incorporated in light-sensitive hydrophilic colloidsilver halide emulsion layers by means of a wide range of coupler-to-solvent ratios.
Still another object of our invention is to provide new uncolored cyan-dye-forming couplers which aiford automatic color correction for the cyan dye image.
3,419,390 Patented Dec. 31, 1968 Another object is to provide new image-forming layers containing our new couplers alone or in a hydrophilic colloid such that the coupler is contiguous to light-sensitive silver halide, ZnO, ZnS, CdS, CdSe, NiS, etc., either with or without a binder.
Still another object is to provide improved cyan dye photographic images and improved multicolor photographic images by the use of these new couplers.
Another object is to provide new dilr'usible cyan imageforming couplers for use in cyan color developer solutions.
Still further objects will be apparent from the following specification and claims.
These and other objects are accomplished according to our invention by the use of our new class of fourequivalent phenolic cyan-dye-forming coupling agents in photographic dye-image-forming systems. The compounds of our invention have good coupling reactivity and a low incidence of color fog. Our couplers are characterized by having at least one phenolic coupling moiety with an aminoalkyl group on the coupling position(s) which is displaced when the coupler reacts with oxidized color developer.
The fact that phenolic compounds containing an aminoalkyl group in the coupling position couple with oxidized color developing agents to form cyan dye is unexpected since it had previously been understood that alkyl groups in the coupling position are not displaceable and dye formation does not take place.
Our new cyan-dye-forming couplers are derived from any of the known phenolic or naphtholic cyan-forming four-equivalent couplers by substituting an aminoalkyl group on the carbon atom in the coupling position of the coupler, the said amino group having at least one hydrogen atom.
Included among the new and improved cyan-dye-forming couplers of our invention are those shown to advantages by the formulas:
I. OH
R! I CHaN The R group in the above formula represents an alkoxy group, either straight or branched chain, particularly those of from 1 to 22 carbon atoms (e.g., ethoxy, isopropoxy, decyloxy, octadecyloxy, docosoxy, etc.), a mono or bicyclic alkoxy group such as cyclohexyloxy, cyclopentoxy, norbornyloxy, etc. The alkoxy group may contain substituent groups such as halogen, nitro, hydroxyl, carboxyl, amino, carboxyl ester, e.g., carbomethoxy, sulfo, sulfo esters, e.g., methoxysulfonyl, alkoxy as hereinabove defined, amide, etc. such that when the R group is a carboxyl or sulfo substituted alkoxy group, the coupler contains sufiicient ballasting to render a dye from said coupler nondiifusing. The R group may also represent an amide group such as acetamido, ethylsulfonamido, N-methylbutyramido, N-propylbenzamido, 4-t-butylbenzamido, carbarnyl, N-octadecylcarbamyl, N,N-dihexylcarbamyl, N-
methyl-N-phenylcarbamyl, 3-pentadecylphenylcarbamyl, sulfamyl, etc., such that when R represents sulfamyl, the coupler contains sufiicient ballasting to render a dye from said coupler nondiffusing. These amide groups may also be substituted with groups such as defined for the substituted alkoxy group in R above (e.g., halogen, nitro, hydroxyl, carboxyl, amino, carboxyl esters, sulfo esters, amide, etc.). The R group represents a hydrogen atom, an alkyl group, either straight or branched chain of from 1 to 22 carbon atoms (e.g., methyl, ethyl, isopropyl, tertiary butyl, dodecyl, docosyl, etc.), a mono or bicyclic alkyl group such cyclopentyl, norbornyl, etc., or an aryl group such as phenyl, napthyl, etc. These groups, i.e., alkyl and aryl, may also be substituted with groups such as defined for the substituted alkoxy groups in R above. The R and R groups each represent the hydrogen atom, a halogen atom, an alkyl, aryl, alkoxy, or amide group as defined in R and R above. The R and R groups may also represent the non-metallic atoms needed to complete a fused ring, such as a 5,6- and 6,6-1nembered isoeyclic and heterocyclic rings, e.g., naphthalene, quinoline, benzothiazole, benzimidazole, etc.
Our phenolic (i.e., phenols and naphthols) couplers are characterized by having an amino alkyl group on the coupling position of the coupler which gives them good coupling reactivity and other valuable properties. These couplers are particularly characterized by the low levels of unwanted color fog produced. Excellent coupling reac tivity is obtained with couplers of our invention when incorporated in emulsion layers without the use of highboiling coupler solvents. When high-boiling solvents are used to disperse these couplers, high dye yield and low color fog are attained over a wide range of coupler-tosolvent ratios. When the ditfusible couplers of our invention are used in color developing solutions, excellent reactivity and good dye yield are achieved.
Included among the couplers of Formulas I and II are the following typical examples used to illustrate but not limit our invention.
( 1 4-aminomethyl-Z-methoxyphenol (2) 4-butylaminomethyl-2-methoxyphenol 3 4-anilinomethyl-2-methoxyphenol (4) 1-hydroxy-4-ethylaminomethyl-Z-naphthamide (5) 2-ethoxy-4-propylaminomethyl-S-acetamido-1- naphthol (6) a,a-iminobis (4-methyl-2-methoxyphenol) (7) 1-hydroxy-4- [N-(4-methoxypheuyl) aminomethyl] N-[5-(2,4-di-t-amylphenoxy) butyl] -2-naphthamide r m A conurcmno-Q-cun-z K/ J Cal-In-Z CHzNH OCH3 (8) 1-hydr0Xy-4- [N- 4-methoxyphenyl aminomethyl] N-octadecyl-N- 3',5-dicarbomethoxy -2-n aphthanilide (9) 1-hydroxy-4- [N- 3-methylphenyl aminomethyl] octadecyl-3 ,5 -dicarboxy-Z-naphthanilide 10) 1-hydroxy-4- (N-methylaminomethyl -2-tetradecyloxy-2naphthanilide 11) 1-hydroxy-4- [N- (p-tolyl aminomethyl] -N-{B-{4- [2- (2,4-di-t-amylphenoxy -5- 3-sulfobenzamido benzarnido] -phenyl} ethyl}-2-naphthamide sodium l2) 2-benzamido-4- [N- (4-butylphenyl) aminomethyl] 5- [a- 2,4-di-t-amylphenoxy) butyramido] phenol (13) 2-hexan amide-4- [N- (4-octadecyloxyphenyl) aminomethyl] -5-tetradecy1sulfonarnidophenol 4 (14) 2- ['y 3-pentadecylphenoxy )butyramido] -4- [N- E-methoxybutyl) aminomethyl] -5-methy1phenol (15 a,m-irninobis{4-methyl-2- ['y-(4-t-butylphenoxy) butyramido] phenol} 16) 2-stearamido-4-[N-propylaminomethyl1-6- phenylphenol 17) 2-octadecyloxy-4-[N- (4-methoxyphenyl) aminomethyl] l-naphthol (18) 5- N-ethylaminomethyl -7-acetarnido-8-hydroxyquinoline (19) 4-hydroxy-5- (N-butylcarb amyl -7-(N-octadecylaminomethyl benzimidazole (20) 1-hydroxy-4-{N- [4-(8-acetamido-3,6-disulfo-1- hydroxy-Z-naphthylazo)phenyl]aminomethyl}-N- ['y-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide disodium salt (21) 1-hydroxy-4- [N-(4-octadecyloxyphenyl)aminomethyl] -N- [B- dimethylsulfamyl) ethyl] -2-naphthamide (22) 1-hydroxy-4-[N-(3-steararnidophenyl)aminomethyl] -2'-methoxy-2-naphthanilide (23 1-hydroxy-4- (N-norbornylaminomethyl -N- 'y- (3-pentadecylphenoxy)butyl]-2-naphthamide The couplers of our invention are distinguished by their high reactivity and the very low density of unwanted color fog that is formed by color development to form dye images from the couplers. The aminoalkyl group provides a means of attaching other substituents to our couplers such as, for example, preformed dyes useful in color correction, and the like. Additional ballasting groups can conveniently be introduced via the aminoalkyl group; these ballasting groups are then eliminated during the coupling reaction with oxidized color developer which forms theimage dyes.
The diffusible couplers of our invention, such as couplers 1-6, and 18, are used to advantage in color developer solutions used to color develop light-sensitive elements used for color photography which do not contain the color-forming coupler. Any of the well known primary aromatic amino color-forming silver halide developing agents such as the phenylenediamines, e.g., diethyl-pphenylenediamine hydrochloride, 'monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, Z-amino-S-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-lauryl)aminotoluene, N-ethyl- 7 f? methanesulfonamidoethyl 3 methyl 4 amino,
aniline, 4-N-ethyl-N-B-hydroxyethylaminoaniline, etc., the p-aminophenols and their substitution products where the amino group is unsubstituted may be used in the alkaline developer solution with our couplers. Various other materials may be included in the developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisulfite, bromide, iodide, etc., and the thickening agents used in viscous developer compositions. The following is a typical developer solution given to illustrate but not limit our invention.
G. Z-amino-4-diethylaminotoluene HCl 2.0 Sodium sulfite (anhydrous) 2.0 Sodium carbonate monohydrate 20.0 Potassium bromide 1.0 Coupler 2.0
Water to 1000.0 ml.
The other coupler examples used to illustrate our invention are nondifliusing and are used to advantage in photographic image-forming layers. Couplers such as 9, 11, illustrate those that are incorporated as Fischertype couplers. The other nondiifusing couplers, e.g., 7, 8, 10, 12, 13, 14, 15, 16, 17 19, 21, 22, 23, are incorporated in emulsion layers by methods such as are described by Mannes et al. U.S. Patent 2,304,939, issued Dec. 15, 1942, Jelley et al., U.S. Patent 2,322,027, issued June 15, 1943, etc., in which high-boiling organic solvents ase used to dissolve the coupler, and by methods described in Vittum et al., U.S. Patent 2,801,170, and Fierke et al., U.S. Patent 2,801,171, both issued July 30, 1957, and Julian, U.S. Patent 2,949,360, issued Aug. 16, 1960, in which low-boiling or water-soluble organic solvents are used with or in place of the high-boiling solvent. The use of such coupler dispersions permits thinner emulsion layers. These thinner layers are very desirable because they cause less light scattering, consequently, they produce sharper images.
Coupler 20 contains a preformed dye attached to the coupler on the phenylaminoalkyl group. This dye is eliminated on the coupling of the coupler with an oxidized color developer and diffuses out of the film. This conpler can be used as a magentacolored coupler for the purpose of correcting for the unwanted green absorption of cyan image dyes, i.e., that formed from the coupler itself as well as that formed from other cyan couplers. Generally, such a coupler as this would be used in combination with another image-forming cyan coupler in the same layer.
Our couplers are used to advantage in the color de velopment of photographic image-forming layers of the developing-out types. The light-sensitive materials used to advantage in our image-forming layers include silver halide (e.g., silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc.), ZnO, ZnS, CdS, CdSe, NiS, etc., either with or without a hydrophilic colloid binder. When incorporated in image-forming layers, our couplers are contiguous with the said light-sensitive material either in the same layer or in a contiguous layer.
Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound. Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in U.S. Patent 2,286,215, a far-hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 1926%, as described in U.S. Patent 2,327,808, a water-soluble ethanolamine cellulose acetate as described in U.S. Patent 2,322,085; a polyacrylamide having a combined acrylamide content of -60% and a specific viscosity of 0.25l.5 or an imidized polyacrylamide of like acrylamide content and viscosity as described in U.S. Patent 2,541,474, zein as described in U.S. Patent 2,563,791, a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in U.S. Patent 2,768,154, or containing cyano-acetyl groups, such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in U.S. Patent 2,808,331, or a polymeric material which results from polymerizing a protein or a saturated acrylated protein with a monomer having a vinyl group as described in U.S. Patent 2,852,382.
The silver halide or other lightsensitive material used in the photographic element of our invention can be chemically sensitized or optically sensitized by any of the accepted procedures.
Usually our emulsion are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support. Usually the support is coated in succession with a redsensitive layer, a green-sensitive layer, and a blue-sensitive layer eirther with or without a Carey Lea filter between the blue-sensitive and green-sensitive layers. The three differently color-sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer. Preferably, these light-sensitive layers are arranged on the same side of the support.
Our invention is further illustrated by the following examples.
EXAMPLE 1 The ability of the phenolic coupling agents of our invention to undergo chromogenic development with oxidized developing agent depends on the elimination of the aminoalkyl group located in the coupling position of the coupling agent. The ease of displacement for two of the couplers of our invention was measured by determining the coupling rate relative to phenol. The results are recorded in Table I. The procedure was that of Tong and Glesmann, J.A.C.S., 79, 583 (1957), using a jet-mixing machine described by W. R. Ruby, Rev. Sci. Instruments, 26, 460 (1955).
TABLE I Group in Coupling Coupling Rate Coupler No. Position k 10 (relative to phenol=1 10 Control H (Guaiacol, control)... CH2NH2 220 CH2NHCHz 240 From the above it can readily be seen that compounds 1 and 6 of our invention are much more reactive than the unsubstituted control, guaiacol.
EXAMPLE 2 A single layer gelatin silver bromoiodide emulsion containing coupler 7 and coupler solvent di-n-butylphthalate was made. This coating contained 10 parts of gelatin, 5 parts of silver, 2 parts of coupler, and 1 part of coupler solvent. A strip of the above mentioned coating was given -second exposure on a 1B intensity scale sensitometer and processed in a conventional manner to a color negative using the following developer solution.
Sodium sulfite (anhydrous) g 2.0 2-amino-S-diethylaminotoluene HCl 2.0 Sodium carbonate monohydrate g 20.0 Potassium bromide g 2.0 Wate to pH 10.86 liter 1.0
The image dye which was formed in the processed strip had a x of 690 m and a l) of 2.4.
This processed strip was then immersed in a ferricyanide bleach bath, and the residual coupler formed a yellow dye image (i.e., positive image) which affords automatic color correction by providing a color-correcting mask for the unwanted blue absorption of the cyan dye image. This yellow mask image had a )t of 477 my. and :a D of 0.4.
Similarly, other couplers of our invention are used to advantage in color photography as illustrated previously with representative couplers. Further, the couplers of our invention are valuable as cyan image-forming couplers in multilayer photographic color films containing other classes of couplers in the other layers of said film. Such other couplers are, for example, magenta-forming pyrazolones, cyanoacetyl coumarones, indazolones, etc., and yellow couplers such as a-acylacetanilides and dibenzoylmethanes.
The preparation of our couplers is illustrated by a description of representative couplers of our invention.
COUPLER 1 A solution of g. of vanillin oxime in 2'00 ml. of ethanol was placed in a bottle of a Burgess-Parr reduction apparatus, 0.2 g. of 10% palladium on carbon catalyst was added, and the mixture shaken at room temperature in an atmosphere of hydrogen under an initial pressure of 50 p.s.i., until the calculated amount was taken up. The catalyst was removed by suction filtration. The filtrate was concentrated to dryness under diminished pressure on a water bath. The crystalline base, melting at 130-132 C., was converted to the hydrochloride and purified by recrystallization from ethanol. The yield of product, melting at 213-214 C., was 8.7 g.
COUPLER 2 A mixture of 15.2 g. of vanillin, 7.3 g. of butylamine, and 60 ml. of ethanol was heated at reflux for minutes. The alcohol was distilled under diminished pressure on a water bath. The oily residue, which could not be induced to crystallize, was dissolved in 250 ml. of ethanol and catalytically reduced in the manner described under coupler 1. The hydrochlorine, after three recrystallizations from acetonitrile, melted at 128129 C. The yield of product was 4.6 g.
COUPLER 3 A mixture of 18.2 g. of 4-hydroxy-3-methoxybenzylidene aniline, prepared from vanillin and aniline by the bnezylidene aniline procedure described in Or-g. Syn. Coll., vol. I, p. 80, O.2-0.3 g. of Raney nickel catalyst in absolute ethanol was reduced in a Parr shaker bottle as described under coupler 1. The hydrochloride, obtained by passing dry hydrogen chloride into a benzene solution of the base after two recrystallizations from acetone methanol (1:1 mixture), melted at 162-163 C. The yield of product was 14 g.
COUPLER 6 A mixture of 16.7 g. of vanillin oxime, 300' ml. of ethanol, and 0.30.5 of Raney nickel catalyst, treated in the manner described under coupler 1 above, gave as the major product, M.P. 245 C. with decomposition.
Couplers 4, 5 and 7 through 23 are prepared by a basic synthesis involving the following steps:
(1) Replacing the hydrogen atom in the 4-position of a 2-substituted phenolic compound with an aldehydric group via a Duff reaction;
(2) tReacting the product of step (1) with an amine to form a Schiff base;
(3) Reducing the Schiif base formed in step (2) to a phenol having an aminomcthyl group in the 4-position.
The foregoing procedure may be formulated as follows:
The four-equivalent image-forming couplers of our invention are distinguished from other four-equivalent couplers by having an aminoalkyl group substituted on the coupling position of the coupler molecule. Our couplers are characterized by not producing color fog, and by having very good coupling reactivity. The couplers of our invention may be used in emulsion layers either alone or admixed with other couplers, either four-equivalent couplers, competing couplers, and the like.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be elfected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
We claim:
1. An image-forming layer containing silver halide and contiguous thereto a coupler which is capable of forming a cyan dye on coupling with the oxidation product of a primary aromatic amino color developing agent, said coupler containing at least one phenolic coupling moiety, said phenolic coupling moiety being substituted in the coupling position with an aminomethyl group, said amino group having at least one hydrogen atom, and said phenolic coupling moiety being substituted in a position ortho to the hydroxyl group with a group selected from the class consisting of an alkoxy group and an amide group, said dye being nondiffusing.
2. An image-forming layer containing silver halide and contiguous thereto a coupler selected from the class consisting of those having the formulas:
OH OH OH I I wherein R represents a group selected from the class consisting of an alkoxy group and an amide group; R represents a group selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group; R and R each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an amide group, and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazoie, said coupler being capable of forming a nondiffusing dye.
3. A light-sensitive hydrophilic colloid silver halide emulsion layer containing 1-hydroxy-4-[N-(4-methoxyphenyl)ampinomethyl] N [fi-(2,4-di-t-amylphenoxy)- butyl]-2-naphthamide.
4. A light-sensitive hydrophilic colloid silver halide emulsion layer containing 1-hydroxy-4-[N-(4-methoxyphenyl)aminomethyl] N octadecyl N-(3,5'-dicarbomethoxy) -2-naphthanilide.
5. A light-sensitive hydrophilic colloid silver halide emulsion layer containing 1 hydroxy 4[N (3-methylpheny)aminomethyl] N-octadecyl 3',5 dicarboXynaphthanilide.
6. A light-sensitive hydrophilic colloid silver halide emulsion layer containing 1-hydroXy-4-(N-methylaminomethyl) -2'-tetradecyloxy-Z-napthanilide.
7. A light-sensitive hydrophilic colloid silver halide emulsion layer containing t d-iminobis{4-methyl-2-[' (4-t-butylphenoxy) butyramido] phenol}.
8. An image-forming layer containing silver halide and contiguous thereto a coupler selected from the class consisting of those having the formula:
wherein R represents a group selected from the class consisting of an alkoxy group and an amide group; R' represents a group selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group; R and R each represents -a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an amide, and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazole, said coupler being capable of forming a nonditiusing dye.
9. An image-forming layer of claim 8 in which the R group of the coupler represents an amide group.
10. An image-forming layer containing silver halide and contiguous thereto a coupler selected from the class consisting of those having the formula:
OH ?H R R R R R R H I I CHz-N-CH:
wherein R represents a group selected from the class consisting of an alkoXy group and an amide group; R and R each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an amide group, and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazole, said coupler being capable of forming a nondittusing dye.
11. A cyan color developer comprising an aqueous alkaline solution containing a primary aromatic amino color developing agent and a ditfusi'ble coupler selected from those having the formulas:
CHaN CH:N-CH1 wherein R represents a group selected from the class consisting of an alkoxy group and an amide group; R' represents a group selected from the class consisting of the hydrogen atom, an alkyl group, and an aryl group; R and R each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an amide group, and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazole, said coupler reacting with oxidized color developing agent to form a nondifiusing dye.
12. A cyan color developer comprising an aqueous alkaline solution containing a primary aromatic amino color developing agent and a diffusible coupler selected from those having the formulas:
OH OH OH wherein R represents a group selected from the class consisting of a lower alkoxy group and the amide group; R represents a group selected from the class consisting of the hydrogen atom, a lower alkyl group and phenyl; R and R each represents a group selected from the class consisting of the hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, phenyl and an amide group and together represent the non-metallic atoms necessary to form a fused ring selected from the class consisting of naphthalene, quinoline, benzothiazole and benzimidazole, said coupler reacting with oxidized color developing agent to form a nondifiusing dye.
13. A cyan color developer comprising an aqueous alkaline solution containing a primary aromatic amino color developing agent and a ditiusible coupler selected from the class consisting of 4-aminomethyl-2-methoxyphenol, 4-butylaminomethyl-Z-methoxyphenol, 4-anilinomethyl-Z-methoxyphenol, 1-hydroxy-4-ethylaminomethyl- 2 naphthamide, 2 ethoxy 4-propylaminomethyl-S-acetamido 1 naphthol, a,a' iminobis (4-methyl-2-methoxyphenol), and S-(N-ethylaminomethyl)-7-acetamido-8-hydroxyquinoline, said coupler reacting with oxidized color developing agent to form a nondifr'using dye.
References Cited UNITED STATES PATENTS 3,227,550 1/1966 Whitmore et a1. 96-100 3,227,551 1/1966 Barr et al. 96-100 3,311,476 3/1967 Loria 96-100 1. TRAVIS BROWN, Primary Examiner.
U.S. Cl. X.R.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dec ember 31 1 Dated I968 Patent N0. 3, 9,39
Inventor) Homer W. J Cres sman and John R Thirtle It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
lines 1 7 through 27 the structural formula reading lolumn 9,
R 2 H B should read I 11 -1 R EN R/R CH N and in line 37 between "amide" and insert -group- Column 1 0, lines 28 through 35, in the s tructural formula on the right -hand side of the column, that part of the structure re adin H I 1 H I I l CH2-CCH2 should read cH Ne1-1 SIGNED AND SEALED MAY 261970 (SEAL) Attest:
WILLIAM E. SGH'UYIIER, JR.
Edward M. Fletcher, It.
Commissioner of Patents L. Attesting Officer
US492904A 1965-05-03 1965-10-04 Elements and developers for color photography utilizing phenolic couplers containingan aminoalkyl group on the coupling position Expired - Lifetime US3419390A (en)

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GB19500/66A GB1153193A (en) 1965-05-03 1966-05-03 Photographic Colour Development Process
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Cited By (7)

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Publication number Priority date Publication date Assignee Title
US3864401A (en) * 1970-12-23 1975-02-04 Merck & Co Inc Substituted 2-aminomethyl-4,6-dihalophenols
US3960958A (en) * 1974-08-26 1976-06-01 Pfizer Inc. 3,4- AND 3,5-Dialkoxybenzylamines
US4028106A (en) * 1974-11-05 1977-06-07 Konishiroku Photo Industry Co., Ltd. Method for developing an exposed silver halide color photosensitive material
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
US5091291A (en) * 1990-10-25 1992-02-25 Eastman Kodak Company Alkyl substituted photographic couplers and photographic elements and processes employing same
EP0574090A1 (en) 1992-06-12 1993-12-15 Eastman Kodak Company One equivalent couplers and low pKa release dyes
EP0711804A2 (en) 1994-11-14 1996-05-15 Ciba-Geigy Ag Latent light stabilizers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3227551A (en) * 1959-04-06 1966-01-04 Eastman Kodak Co Photographic color reproduction process and element
US3227550A (en) * 1962-09-07 1966-01-04 Eastman Kodak Co Photographic color reproduction process and element
US3311476A (en) * 1962-12-26 1967-03-28 Eastman Kodak Co Two-equivalent couplers for color photography

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3227551A (en) * 1959-04-06 1966-01-04 Eastman Kodak Co Photographic color reproduction process and element
US3227550A (en) * 1962-09-07 1966-01-04 Eastman Kodak Co Photographic color reproduction process and element
US3311476A (en) * 1962-12-26 1967-03-28 Eastman Kodak Co Two-equivalent couplers for color photography

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864401A (en) * 1970-12-23 1975-02-04 Merck & Co Inc Substituted 2-aminomethyl-4,6-dihalophenols
US3960958A (en) * 1974-08-26 1976-06-01 Pfizer Inc. 3,4- AND 3,5-Dialkoxybenzylamines
US4028106A (en) * 1974-11-05 1977-06-07 Konishiroku Photo Industry Co., Ltd. Method for developing an exposed silver halide color photosensitive material
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
US5091291A (en) * 1990-10-25 1992-02-25 Eastman Kodak Company Alkyl substituted photographic couplers and photographic elements and processes employing same
EP0574090A1 (en) 1992-06-12 1993-12-15 Eastman Kodak Company One equivalent couplers and low pKa release dyes
EP0711804A2 (en) 1994-11-14 1996-05-15 Ciba-Geigy Ag Latent light stabilizers

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