WO1992021064A1 - Colorants filtrants bloques pour materiel et procede photographiques - Google Patents

Colorants filtrants bloques pour materiel et procede photographiques Download PDF

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Publication number
WO1992021064A1
WO1992021064A1 PCT/US1992/004062 US9204062W WO9221064A1 WO 1992021064 A1 WO1992021064 A1 WO 1992021064A1 US 9204062 W US9204062 W US 9204062W WO 9221064 A1 WO9221064 A1 WO 9221064A1
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WIPO (PCT)
Prior art keywords
unsubstituted
substituted
group
photographically useful
alkyl
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PCT/US1992/004062
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English (en)
Inventor
Jared B. Mooberry
James Siefert
Daniel L. Kapp
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Eastman Kodak Company
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Publication date
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Publication of WO1992021064A1 publication Critical patent/WO1992021064A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • C09B29/0007—Monoazo dyes prepared by diazotising and coupling from diazotized anilines containing acid groups, e.g. CO2H, SO3H, PO3H2, OSO3H, OPO2H2; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0801—Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls
    • C09B29/0802—Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls containing COOH
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C09B29/103—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the naphthalene series
    • C09B29/106—Hydroxy carboxylic acids of the naphthalene series
    • 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

Definitions

  • This invention relates to a new blocked photographically useful compound that is capable of more rapidly releasing the photographically useful group of the compound upon reaction of the compound with a dinucleophile reagent.
  • the invention relates to a new blocked filter dye.
  • Couplers and dyes are known in the photographic art that contain a blocking group and that are capable of being released or unblocked upon processing of the photographic material containing the compound.
  • blocking groups have been described in, for example, U.S. Patents 4,690,885; 4,358,525 and 4,554,243. While these compounds have enabled increased storage stability compared to compounds that are not blocked and have provided release of the photographically useful group from the compound upon processing, often the stability of the compounds during storage prior to exposure and processing of the photographic materials containing the compounds has not been entirely satisfactory and the rate of release or unblocking of the compound has been less than desired.
  • Filter dyes are used in a variety of photographic products to absorb unwanted light.
  • a yellow filter dye or colloidal yellow silver may be placed between the blue and green light-sensitive layers to filter out unwanted blue light and prevent exposure of the green layer. They may be used in antihalation layers to absorb light reflected, for instance, from the support, which would lead to undesired exposure of light-sensitive layers. They may also be used within light-sensitive layers as intergrain absorbers to enhance sharpness by absorbing light reflected from grains of silver halide. These dyes are generally removed during the development process, either by washing out or by reacting with processing chemicals to be decolorized or otherwise destroyed.
  • filter dye moieties which are immobilized prior to processing by attachment to a blocking group and are made mobile or diffusible during the process by cleavage from the blocking group.
  • the diffusible filter dye moiety released by unblocking can be washed out of the film or be destroyed by the water-soluble nucleophiles such as hydroxide and sulfite in the processing solution.
  • the blocking group is effectively immobilized by ballasting either the blocking group itself or the timing group (or timing groups) which may be used to connect the dye moiety to the blocking group.
  • the present invention solves these problems by providing a photographic element comprising a support bearing at least one photographic silver halide emulsion layer and a blocked photographically useful compound comprising a photographically useful group (PUG), in particular a filter dye, and a new blocking group that is capable of releasing the PUG upon processing the photographic element
  • the blocking group comprises two electrophilic groups, the least electrophilic of which is bonded directly or through a timing group to the photographically useful group (PUG), and (b) is capable of reacting with a dinucleophile; and wherein (c) the two electrophilic groups are separated from each other by a bond or unsubstituted or substituted atom that enables a nucleophilic displacement reaction to occur with release of the PUG upon processing the photographic element in the presence of a dinucleophile reagent.
  • a preferred blocked photographically useful compound as described is represented by the formula:
  • E1 and E2 are independently electrophilic groups, wherein E1 is more electrophilic than E2;
  • T1 and T2 are individually releasable timing groups
  • Y1 is an unsubstituted or substituted atom, preferably a carbon or nitrogen atom, that provides a distance between E1 and E2 that enables a nucleophilic displacement reaction to occur with release of the PUG upon processing a photographic element containing the blocked photographically useful compound in the presence of a dinucleophile;
  • PUG is a photographically useful group capable of being released upon processing the photographically useful compound
  • w, x and y are independently 0 or 1;
  • n 1 or 2.
  • R 3 is. unsubstituted or substituted C(1- 4)alkyl, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl, unsubstituted or substituted alkaryl, unsubstituted or substituted alkoxyaryl, a ballast group, or the atoms necessary with Z to complete a ring with Y 2 ,
  • Z represents the atoms necessary to complete a ring with R 3 and Y 2 ,
  • Y 2 is a substituted or unsubstituted carbon or nitrogen atom that provides a distance between the carbonyl groups that enables a nucleophilic displacement reaction to occur upon processing a photographic element containing the blocked photographically useful compound in the presence of a dinucleophile, q is 0 or 1,
  • T3 is a releasable timing group which is unballasted or ballasted
  • PUG is a photographically useful group, in particular a filter dye.
  • R 4 and R 4c individually are unsubstituted or substituted C(1-4)alkyl, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl, unsubstituted or substituted alkaryl, unsubstituted or substituted alkoxyaryl, or a ballast group,
  • R 4a and R 4b individually are unsubstituted or substituted C(1-4) alkyl, unsubstituted or substituted aryl, or a ballast group
  • PUG is a filter dye
  • T 4 and T 5 are individually releasable timing groups which are unballasted or ballasted, and
  • r and s individually are 0 or 1.
  • R 4 , R 4a , R 4b and R 4c are methyl.
  • R, and R 4c individually are ballast groups as described above. Ballast groups, i.e., groups that decrease the rate of diffusion, are known per se. Exemplary ballast groups are described, e.g., in U.S. Patent No. 4,923,789, col. 7, which is incorporated by reference.
  • the ballast groups R 4 according to the instant invention preferably are long-chain
  • ballast groups R 4c preferably are alkyl or alkaryl groups, which can be further modified, e.g., by the substitution of a sulfonamide (-NHSO 2 -) group for a -CH 2 - group which is not adjacent to the carbonyl group.
  • a preferred R 4c ballast group is a benzyl sulfonamide group.
  • process-cleavable ballast denotes a ballast group that is attached to the timing group or blocking group, and that is removed from the PUG, here the filter dye, as a function of the deblocking process.
  • One embodiment of the invention is a photographic element comprising a blocked photographically useful compound, in particular a filter dye, containing the new blocking group as described. Another embodiment is a process of forming a photographic image by developing an exposed photographic element as described in the presence of a dinucleophile reagent. A further embodiment is a new photographically useful compound, in particular a filter dye, containing the new blocking group as described.
  • FIG. 1 is a plot of density vs. wavelength for filter dyes according to the invention compared to CLS.
  • the blocked photographically useful compounds enable both improved storage stability and more rapid release upon processing of a photographic element containing such a compound. Both of these properties are achieved by the blocked photographically useful compounds as described due at least in part to the particular structure of the new blocking group.
  • the blocked photographically useful compounds of the invention do not release the photographically useful groups of the compound upon reaction with a nucleophilic compound containing only one nucleophilic group.
  • nucleophilic compound containing two nucleophile groups described herein as a dinucleophile reagent, such as hydroxylamines, hydrogen peroxide, hydrazine, diamines and substituted hydrazines.
  • a nucleophilic compound containing two nucleophile groups such as hydroxylamines, hydrogen peroxide, hydrazine, diamines and substituted hydrazines.
  • Carbonyl groups are preferred electrophilic groups in the new blocking groups as described.
  • the new blocking group structure resists reaction with nucleophilic compounds containing only one nucleophilic group.
  • reaction of a nucleophilic compound containing only one nucleophilic group at E1 in the case of a carbonyl group would lead to adducts in which the hydroxyl group generated can internally react with E2 only by a three or four member ring that is very difficult to form.
  • only compounds, such as water, that contain one nucleophilic group are encountered in storage of photographic silver halide elements. Such compounds would not release the blocking group of the invention as described.
  • the release of the blocking group can be initiated by reaction of the blocking group with an appropriate dinucleophile reagent.
  • the selection of an appropriate dinucleophile reagent preferably enables formation of a five- or six-member ring compound.
  • the initiation of deblocking can take place by reacting the particular dinucleophile reagent at concentrations and under conditions that enable the desired rate of release.
  • the dinucleophile herein means a compound represented by the formula:
  • Nu1 and Nu2 individually are nucleophilic N, O, S,
  • X 1 is a chain of j atoms wherein j is 0, 1 or 2.
  • Preferred dinucleophile reagents are hydroxy la ⁇ i ne, hydrogen peroxide, and monosubstituted hydroxylamine.
  • the dinucleophile reagent herein also includes a salt form of the reagent, such as the acid salts, for example, sulfate or bisulfite salts.
  • the term photographically useful group refers to any group that can be used in a photographic material and that can be released from the blocking group as described. It refers to the part of the blocked photographically useful compound other than the blocking group.
  • the PUG can be, for example, a photographic dye, which can be diffusible or non-diffusible, or a photographic reagent.
  • a photographic reagent herein is a moiety that upon release further reacts with components in the photographic element.
  • Such photographically useful groups include, for example, couplers (such as, image dye-forming couplers, development inhibitor releasing couplers, competing couplers, polymeric couplers and other forms of couplers), development inhibitors, bleach accelerators, bleach inhibitors, inhibitor releasing developers, dye precursors, developing agents (such as competing developing agents, dye-forming developing agents, developing agent precursors, and silver halide developing agents), silver ion fixing agents, silver halide solvents, silver halide complexing agents, image toners, pre-processing and post-processing image stabilizers, hardeners, tanning agents, fogging agents, antifoggants, ultraviolet radiation absorbers, nucleators, chemical and spectral sensitizers or desensitizers, surfactants, and precursors thereof and other addenda known to be useful in photographic materials.
  • couplers such as, image dye-forming couplers, development inhibitor releasing couplers, competing couplers, polymeric couplers and other forms of couplers
  • development inhibitors such as
  • the PUG can be present in the photographically useful compound as a preformed species or as a precursor.
  • a preformed development inhibitor may be bonded to the blocking group or the development inhibitor may be attached to a timing group that is released at a particular time and location in the photographic material.
  • the PUG may be, for example, a preformed dye or a compound that forms a dye after release from the blocking group.
  • PUG is a filter dye.
  • the photographically useful compound can optionally contain at least one releasable timing group (T) between the PUG and the blocking group as described.
  • T releasable timing group
  • the reaction of the photographically useful compound with a dinucleophile reagent can seguentially release the blocking group from the timing group and then the timing group can be released from the PUG.
  • the term "timing group” herein also includes a linking group that involves little or no observable time in the release action. This can occur in, for example, the development step of an exposed photographic element when the developer composition comprises a dinucleophile reagent, such as a hydroxylamine. Any timing group that is known in the photographic art is useful as the timing group between the PUG and the blocking group in the present invention. Examples of useful timing groups are described in, for example. U.S. Patents 4,248,962 and 4,409,323 and European Patent Application 255,085.
  • timing groups employed including the linkage by which they are attached to the PUG and the blocking group and the nature of the substituents on the timing group (e.g., ballast groups) can be varied to help control such parameters as rate and time of bond cleavage of the blocking group and the PUG as well as diffusibility of the PUG and substituent groups.
  • the substituents on the timing group can be varied to control the diffusibility or mobility of the timing group itself as well as the PUG.
  • a substituent on the timing group can constitute a ballast to prevent diffusion of the filter dye moiety until release from the timing group.
  • the cleavage of the bond between the timing group and the blocking group releases the timing group and the PUG as a unit.
  • the particular timing group in this case can control the rate and distance of diffusion in the photographic material before the PUG is released from the timing group.
  • the timing group should not contain a structure that inhibits the reaction of the blocking group with a dinucleophile reagent.
  • timing groups T 1 and T 2 are independently selected to provide the desired rate and time of release of the PUG upon processing.
  • the timing groups T 1 and T 2 can be the same or different. Examples of preferred timing groups for T 1 and T 2 are as follows:
  • R 1d , R 1c , and R 1f are hydrogen or substituents, such as alkyl, nitro, chloro, sulfonamido, or ballasted substituents such as long chain alkyl (containing 5 to 40 carbon atoms), long chain alkyl or alkaryl sulfonamido or amido, etc.
  • timing groups are described in, for example, U.S. Patent 4,248,962 and U.S. 4,772,537.
  • the two electrophilic groups, E 1 and E 2 can be any electrophilic group that enables nucleophilic displacement reaction to occur upon reaction of the blocking group with dinucleophile reagent. While carbonyl groups are highly preferred as the electrophilic groups, other examples of useful electrophilic groups are as follows:
  • R f is a substituent that causes the attached carbon atom to be an electrophilic center.
  • R q is alkyl, such as methyl, ethyl, n-propyl, i-propyl, and butyl, or aryl, such as phenyl, benzyl or substituted phenyl or other substituents such as alkoxy, chloro and amido, as well as ballasted substituents such as long chain alkyl or alkaryl; and,
  • R 4 is as described; R 4a and R 4b are individually as described, such as methyl, ethyl, n-propyl, i-propyl, butyl, phenyl, benzyl, and substituted phenyl, or other substituents such as alkoxy, chloro and araido, which can also be ballasted.
  • the PUG is a filter dye.
  • the blocked filter dyes as described can be used in photographic materials and in ways that filter dyes have been used in the photographic art.
  • Photographic elements according to the invention can be processed by conventional technigues in which color forming couplers and color developing agents are incorporated in separate processing solutions or compositions or in the photographic element.
  • blocked color developing agents can be incorporated in the photographic element and simplified processing solutions used for processing the element.
  • the photographic elements can be single color elements or multicolor elements.
  • Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the visible spectrum.
  • Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
  • the layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the photographic art.
  • the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer, such as by the use of microvessels as described in U.S. Patent 4,362,806.
  • a typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green- sensitive silver halide emulsion layer having associated therewith at least one magenta dye- forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.
  • the element can contain added layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like.
  • the blocked photographically useful compounds as described can be present in and/or associated with one or more of the layers of the photographic element.
  • the compounds can be in an emulsion layer and/or in an adjacent layer.
  • the silver halide emulsions employed in the elements can be comprised of silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • the emulsions can include coarse, medium or fine silver halide grains.
  • High aspect ratio tabular grain emulsions are specifically contemplated, such as those described by Mignot U.S. Patent 4,386,156, Wey U.S. Patent 4,399,215, Maskasky U.S. Patent 4,400,463, Wey et al. U.S. Patent 4,414,306, Daubendiek et al. U.S.
  • Patent 4,414,310 Solberg et al. U.S. Patent 4,433,048, Wilgus U.S Patent 4,434,226, Maskasky U.S. Patent 4,435,501, Evans et al. U.S. Patent 4,504,570, Maskasky U.S. Patent 4,643,966, and Daubendiek et al. U.S. Patents 4,672,027 and 4,693,964.
  • silver bromoiodide grains with a higher molar proportion of iodide in the core of the grain than in the periphery of the grain such as those described in US 4,379,837; US 4,444,877; US 4,565,778; US 4,636,461; US 4,665,012; US 4,668,614; US 4,686,178; US 4,728,602; GB 1,027,146; JA 54/48,521; and EP 264,954.
  • the silver halide emulsions can be either monodisperse or polydisperse as precipitated.
  • the grain size distribution of the emulsions can be controlled by silver halide grain separation technigues or by blending silver halide emulsions of differing grain sizes.
  • Sensitizing compounds such as compounds of copper, thallium, lead, bismuth, cadmium and Group VIII noble metals, can be present during precipitation of the silver halide emulsion.
  • the emulsions can be surface-sensitive emulsions, that is, emulsions that form latent images primarily on the surfaces of the silver halide grains, or internal latent image-forming emulsions, that is, emulsions that form latent images predominantly in the interior of the silver halide grains.
  • the emulsions can be negative- working emulsions, such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or direct-positive emulsions of the unfogged, internal latent image-forming type, which are positive-working when development is conducted with uniform light exposure or in the presence of a nucleating agent.
  • the silver halide emulsions can be surface sensitized.
  • Noble metal e.g., gold
  • middle chalcogen e.g., sulfur, selenium, or tellurium
  • reduction sensitizers employed individually or in combination, are specifically contemplated.
  • Typical chemical sensitizers are listed in Research Disclosure, Item 17643, cited above, Section III.
  • the silver halide emulsions can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra-, and poly-nuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls, and strepto-cyanines.
  • Illustrative spectral sensitizing dyes are disclosed in Research Disclosure. Item 17643, cited above, Section IV.
  • Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure. Item 17643, Section IX and the publications cited therein.
  • the elements of this invention can include additional couplers as described in Research Disclosure Section VII, paragraphs D, E, F and G and the publications cited therein. These additional couplers can be incorporated as described in Research Disclosure Section VII, paragraph C and the publications cited therein.
  • the photographic elements of this invention can contain brighteners (Research Disclosure Section V), antifoggants and stabilizers (Research Disclosure Section VI), antistain agents and image dye stabilizers (Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (Research Disclosure Section VIII), hardeners (Research Disclosure Section X), coating aids (Research Disclosure Section XI), plasticizers and lubricants (Research Disclosure Section XII), antistatic agents (Research Disclosure Section XIII), matting agents (Research Disclosure Section XVI) and development modifiers (Research Disclosure Section XXI).
  • the photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.
  • Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX.
  • Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
  • Preferred color developing agents are p- phenylene diamines.
  • Preferred color developing agents are 4- amino-3-methyl-N,N-diethylaniline hydrochloride, 4- amino-3-methyl-N-ethyl-N- ⁇ -(methanesulfonamido)- ethylaniline sulfate hydrate, 4-amino-3-methyl-N- ethyl-N- ⁇ -hydroxyethylaniline sulfate, 4-amino-3- ⁇ -
  • the processing step described above provides a negative image.
  • the described elements are preferably processed in the known C-41 color process as described in, for example, the British Journal of Photography Annual of 1988, pages 196 - 198.
  • the color development step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniformly fogging the element to render unexposed silver halide developable.
  • a direct positive emulsion can be employed to obtain a positive image.
  • the described dinucleophile reagent such as a hydroxylamine
  • the concentration of the dinucleophile reagent in the processing solution can vary depending on such factors as the particular processing solution components, the particular dinucleophile reagent, the processing time and temperature, the particular photographic element to be processed, the desired image and the like.
  • the concentration of the dinucleophile reagent is typically within the range of 10 -5 moles to 1 mole per liter of solution.
  • the blocked photographically useful compounds according to the invention can be prepared by methods and steps known in the organic compound synthesis art.
  • a typical method of preparing a blocked photographically useful compound is as follows: Synthesis I: Preparation of an intermediate
  • This illustrative intermediate compound G1 can be reacted with a photographically useful group (PUG) to provide a blocked photographically useful compound as described.
  • PUG photographically useful group
  • Methyl iodide (32 ml, 0.5 mole) was added via the addition funnel while the temperature rose to about 10oC.
  • the ice bath was replaced with a water bath at room temperature (20oC) before stirring the mixture for an additional 30 minutes while potassium iodide precipitated.
  • the mixture was cooled again to 0oC before adding more methyl iodide (40 ml) and then potassium t-butoxide (56 g, 0.5 mole) (temp. ⁇ 30°C).
  • the mixture was stirred at room temperature for 48 hours and then diluted with about 1 liter of water and 0.5 liter of saturated NaCl solution before the mixture was extracted with ether.
  • the ether solution was washed with 0.1N NaOH and then with IN HCl, dried over magnesium sulfate, and concentrated to an oil.
  • the crude dimethylated ethyl acetoacetate 64 g, 81% yield
  • the crude dimethylated ester 64 g, approx. 0.4 mole
  • NaOH 48 g, 1.2 mole
  • water 320 ml
  • a trace of indicator dye Metal Yellow
  • 3-Amino-4-hydroxybenzyl alcohol (34.8 g, 0.25 mole, prepared as in U.S. Patent No. 4,840,884, incorporated by reference) was completely dissolved in pyridine (200 ml) in a 500 ml flask fitted with addition funnel, thermometer and mechanical stirrer. After cooling in ice, the mixture was treated with a solution of hexadecane sulfonyl chloride (81.2 g, 0.25 mole in 250 ml THF) dropwise over about 30 minutes. The mixture was allowed to warm to room temperature over 1 hour, and then diluted with one liter of water. The precipitated product was filtered, washed with water and dried to yield 95 g (89%) of (A).
  • the sulfonamide (A) (42.7 g, 0.1 mole) was dissolved in a mixture of pyridine (100 ml), THF (600 ml) and triethylamine (28 ml, 0.2 mole) and then cooled in an ice bath.
  • Acid chloride blocking reagent (G1) (14.9 g, 0.1 mole in 100 ml dichloromethane) was added dropwise over about 15 minutes. The mixture was allowed to warm to room temperature over about 1 hour, then diluted with a mixture of 900 ml dichloromethane, washed with aqueous HCl (150 ml cone. HCl in 1.5 1 water) and then with water.
  • the organic layer was dried with MgSO 4 and concentrated to a solid. The solid was then extracted with dichloromethane (250 ml), and the extract was concentrated to a syrup which crystallized from heptane to yield 38.5 g (71%) of
  • Coupler (D) (2.5 g, 3.6 mmole) was dissolved in a mixture of THF (20 ml), acetic acid (10 ml), pyridine (5 ml) and water (5 ml) and then cooled in an ice bath.
  • Diazonium solution was prepared by dissolving 3-aminobenzoic acid (493 mg, 3.6 mmole) in HCl (15 ml, 2N) at 0oC, adding NaNO 2 (248 mg, 3.6 mmole), and stirring for 5 minutes. This solution was added to the solution of coupler (D) and stirred for about 30 minutes, then warmed to room temperature. The precipitate was collected, dissolved in dichloromethane, washed with water, dried, and concentrated to a syrup which crystallized from methanol to yield filter dye (E) (2.0 g).
  • the methyl ester (F) (50 g, 0.115 mole) was dissolved in THF (200 ml) and methanol (100 ml) and treated with NaOH (11.5 g, 0.29 mole in 30 ml of water). After stirring for about 30 minutes, the mixture was diluted with 250 ml of ethyl acetate, washed with 150 ml of 2N HCl and then with water, dried and concentrated to a syrup product acid (G) (49 g).
  • Amido alcohol (H) (53.7 g, 0.1 mole), acid chloride (G2) (22.5 g, 0.1 mole) and THF (200 ml) were combined and cooled in ice. Triethylamine (28 ml, 0.2 mole) was added dropwise over about 20 minutes with vigorous stirring. The mixture was allowed to come to room temperature, then diluted with ethyl acetate, washed with excess IN HCl and then water, dried, concentrated and chromatographed using the same eluent as for (H). Ester alcohol (I) was obtained (35 g).
  • Filter dye (L) (2 g, 1.8 mmole) was dissolved in 15 ml of dichloromethane and 5 ml of trifluoroacetic acid and allowed to stand at room temperature for about 15 minutes until ester cleavage was complete as shown by TLC (same eluent as above). The mixture was washed seguentially with excess IN NaCO 3 , water, IN HCl, and water, and then dried over MgSO 4 and concentrated to solid filter dye (M) (1.3 g). The nmr spectrum in deuterodimethylsulfoxide confirmed the structural integrity of the ballasted filter dye.
  • blocked filter dyes are exemplary of compounds that can be prepared by the methods described. These blocked compounds can be incorporated and processed in a photographic element as described in Example 1.
  • Photographic elements were prepared by coating the following layers on a cellulose acetate film support (amounts of each compound are in rag/nr):
  • Emulsion Layer :
  • magenta image coupler (dispersed in tritolyl phosphate) (619)
  • filter dye compound of the invention dispersed in diethyldodecanamide and coated at 0.215 millimoles/m 2 .
  • a comparison coating containing 43-04 mg/m 2 of Carey Lea Silver (CLS, also called yellow colloidal silver) was prepared. This level of Carey Lea Silver gave approximately the same amount of blue light absorption as the filter dyes of the Example.
  • magenta image coupler The structure of the magenta image coupler is as follows:
  • Each photographic element was imagewise exposed to light through a graduated density test object in a commercial sensitometer to provide a developable latent image (3000°K light source, 0-4 step wedge, with Wratten(TM) 12 plus 0.1ND filter).
  • the resulting photographic films were processed using the following color developer solutions, then stopped, bleached, fixed, washed, and dried to produce stepped colored images.
  • Color Developing Solution :
  • the density of the film to blue and green light in areas of low exposure can be seen in Table I.
  • Db and Dg refer to the densities to blue and green light in areas of minimum exposure after processing using the Color Developer Solution
  • Db without HAS refers to the density to blue light in areas of minimum exposure after processing using Color Developer without HAS.

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  • Organic Chemistry (AREA)
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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

Nouveau colorant filtrant bloqué comprenant un nouveau groupe de blocage qui (a) comporte deux groupes électrophiles dont le moins électrophile est lié directement ou par l'intermédiaire d'un groupe de synchronisation au groupe de colorant filtrant du composé, et (b) est capable de réagir avec un réactif dinucléophile, (c) les deux groupes électrophiles étant séparés l'un de l'autre par une liaison ou un atome non substitué ou substitué qui permet au déplacement nucléophile de se produire avec une libération du colorant filtrant lorsque le composé est mis en réaction avec un réactif dinucléophile. Le colorant filtrant bloqué de la présente invention est utile pour un matériau et un procédé photographique afin de fournir une stabilité accrue et de permettre une libération plus rapide du colorant filtrant lors de la réaction avec un réactif dinucléophile.
PCT/US1992/004062 1991-05-14 1992-05-13 Colorants filtrants bloques pour materiel et procede photographiques WO1992021064A1 (fr)

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US70000691A 1991-05-14 1991-05-14
US700,006 1991-05-14

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WO1992021064A1 true WO1992021064A1 (fr) 1992-11-26

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0684512A1 (fr) * 1994-05-27 1995-11-29 Eastman Kodak Company Eléments photographiques contenant des composés libérés
US5719014A (en) * 1995-10-31 1998-02-17 Eastman Kodak Company Color negative films containing yellow methine dyes for filtration and density correction
US5725999A (en) * 1995-10-31 1998-03-10 Eastman Kodak Company Methine yellow density correction dyes for color negative films with magnetic recording layers
US5800971A (en) * 1995-10-31 1998-09-01 Eastman Kodak Company Photographic element containing codispersions of yellow methine filter or density correction dyes and reducing agents
EP0556920B1 (fr) * 1992-02-19 1998-12-23 Eastman Kodak Company Polymères pour la libération de groupes photographiques utiles
US6057085A (en) * 1997-11-24 2000-05-02 Agfa-Gevaert Nv Color photographic recording material
EP2107122A1 (fr) 2008-03-31 2009-10-07 FUJIFILM Corporation Matériau de détection de protéase, ensemble de matériaux de détection de protéase, et procédé de mesure de protéase

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988004794A1 (fr) * 1986-12-23 1988-06-30 Eastman Kodak Company Colorants de filtrage consistant en une dispersion de particules solides pour compositions photographiques
EP0313308A2 (fr) * 1987-10-19 1989-04-26 EASTMAN KODAK COMPANY (a New Jersey corporation) Elément photographique et procédé comprenant un groupe libérant un colorant
EP0351593A2 (fr) * 1988-06-30 1990-01-24 Eastman Kodak Company Elément photographique manipulable à la lumière avec une couche contenant une dispersion de particules solides de colorant filtre
EP0394974A2 (fr) * 1989-04-26 1990-10-31 Eastman Kodak Company Matériau et procédé photographique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988004794A1 (fr) * 1986-12-23 1988-06-30 Eastman Kodak Company Colorants de filtrage consistant en une dispersion de particules solides pour compositions photographiques
EP0313308A2 (fr) * 1987-10-19 1989-04-26 EASTMAN KODAK COMPANY (a New Jersey corporation) Elément photographique et procédé comprenant un groupe libérant un colorant
EP0351593A2 (fr) * 1988-06-30 1990-01-24 Eastman Kodak Company Elément photographique manipulable à la lumière avec une couche contenant une dispersion de particules solides de colorant filtre
EP0394974A2 (fr) * 1989-04-26 1990-10-31 Eastman Kodak Company Matériau et procédé photographique

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0556920B1 (fr) * 1992-02-19 1998-12-23 Eastman Kodak Company Polymères pour la libération de groupes photographiques utiles
EP0684512A1 (fr) * 1994-05-27 1995-11-29 Eastman Kodak Company Eléments photographiques contenant des composés libérés
US5567577A (en) * 1994-05-27 1996-10-22 Eastman Kodak Company Photographic elements containing release compounds
US5719014A (en) * 1995-10-31 1998-02-17 Eastman Kodak Company Color negative films containing yellow methine dyes for filtration and density correction
US5725999A (en) * 1995-10-31 1998-03-10 Eastman Kodak Company Methine yellow density correction dyes for color negative films with magnetic recording layers
US5800971A (en) * 1995-10-31 1998-09-01 Eastman Kodak Company Photographic element containing codispersions of yellow methine filter or density correction dyes and reducing agents
US6057085A (en) * 1997-11-24 2000-05-02 Agfa-Gevaert Nv Color photographic recording material
EP2107122A1 (fr) 2008-03-31 2009-10-07 FUJIFILM Corporation Matériau de détection de protéase, ensemble de matériaux de détection de protéase, et procédé de mesure de protéase

Also Published As

Publication number Publication date
JPH06500648A (ja) 1994-01-20
EP0540729A1 (fr) 1993-05-12

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