US3326681A - Photographic products and processes - Google Patents

Photographic products and processes Download PDF

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Publication number
US3326681A
US3326681A US305857A US30585763A US3326681A US 3326681 A US3326681 A US 3326681A US 305857 A US305857 A US 305857A US 30585763 A US30585763 A US 30585763A US 3326681 A US3326681 A US 3326681A
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Prior art keywords
silver halide
image
emulsion
dye
yellow
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US305857A
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Vlvian K Walworth
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Polaroid Corp
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Polaroid Corp
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Priority to NL127569D priority Critical patent/NL127569C/xx
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority to US305857A priority patent/US3326681A/en
Priority to FR985027A priority patent/FR1406208A/fr
Priority to NL6409622A priority patent/NL6409622A/xx
Priority to BE652267D priority patent/BE652267A/xx
Priority to DEJ26472A priority patent/DE1285302B/de
Priority to GB35394/64A priority patent/GB1080228A/en
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Publication of US3326681A publication Critical patent/US3326681A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D263/57—Aryl or substituted aryl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/10—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D293/12—Selenazoles; Hydrogenated selenazoles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • 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

Definitions

  • the present invention relates to photography and, more particularly, to photographic products and processes.
  • Another object of the present invention is to provide novel photosensitive elements, comprising not less than one silver halide emulsion, possessing increased speed and improved stability.
  • a further object of the present invention is to provide novel compositions, processes and products for obtaining silver, monochromatic and multichromatic images by photographic diffusion transfer processes which exhibit increased transfer image densities and improved high lights and light steps.
  • a still further object of the present invention is to provide compounds which are not only excellent stabilizers or antifogging agents for light-sensitive silver halide emulsions, but, in addition, have the faculty of performing this function without lowering the sensitivity of the emulsion with which they are associated and without reducing the sensitivity of the emulsion to light of longer wave lengths attributable to the presence of optical sensitizing dyes.
  • a still further object of the present invention is to provide stabilized light-sensitive silver halide emulsions, especially silver halide emulsions exhibiting increased stability against the effects of dry and moist heat.
  • a still further object of the present invention is to provide novel photographic elements, comprising not less than one silver halide emulsion having associated therewith not less than one contiguous layer containing specified color image-forming components, which exhibit increased stability against the effects of dry and moist heat.
  • a still further object of the present invention is to provide novel photographic elements, comprising not less than one silver halide emulsion having associated therewith not less than one contiguous layer containing specified color image-forming components, particularly adapted for employment in multichromatic photographic transfer processes, employing integral multilayer photosensitive elements, to provide improved color separation.
  • a still further object of the present invention is to provide novel photographic elements, comprising not less than one silver halide emulsion having associated therewith not less than one contiguous layer containing specified color image-forming components, which exhibit excellent stability without detachable loss in sensitivity of the emulsion to light of longer wave lengths attributable to the incorporation of optical sensitizing dyes therein.
  • a still further object of the present invention is to provide methods particularly adapted to prepare stabilized photosensitive silver halide emulsions.
  • the invention accordingly comprises the process involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the product possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • cycloammonium quaternary salts that is, N-carboxyalkyl and N-sulfoalkyl substituted azoles containing an oxygen, sulfur or selenium atom as a component of the azole ring
  • the aromatic ring system of the formula may contain the substituents usual in the art, for example, substituents such as lower alkyl, lower alkoxy, phenyl, benzyl, chloro, bromo, iodo, amino, hydroxyl, fused benzene ring,-etc., radicals.
  • acyclic groups of the formula mention may be made of lower alkyl groups comprising from 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, etc., and, as exmaples of preferred cyclic groups, mention may be of aromatic radicals of the henzene series such as a phenyl group.
  • the anion represented by the designation Z in the formula, comprises those anionic acid radicals customary in the art, for example, chloride, bromide, iodide, ptoluenesulfate, acetate, propionate, cyanate, perchlorate, nitrate, sulfate, etc.
  • agents employed in accordance with the present invention may also be used in combination with additional known antifoggants and stabilizers and, where desired, may be included in the processing composition employed for the development, etc., of a photoexposed silver halide emulsion.
  • the optimum concentration of the agent to be employed should be determined empirically for each specific photographic system. However, it has been experimentally determined that, in general, the preferred concentration falls within the range of about 0.005 to 5.0 milligrams per millimole of silver halide present in the silver halide emulsion, depending upon the fogging characteristics of the silver halide emulsion to be stabilized.
  • concentrations in excess of the first-mentioned range may be employed, increasing the concentration beyond the designated limits generally provides no additional beneficial results. Conversely, concentrations below that of the designated range, however, merely decrease stabilization below the effective level generally sought but do not obliterate obtaining beneficial stabilization results. Where desired, however, substantial quantities of the agent may be employed without introducing serious desensitizing effects.
  • Example 1 11.5 g. of a silver iodobromide emulsion containing approximately 12% silver and 9% gelatine was combined with 12 cc. of distilled water. A 2 cc. solution of each of the antifoggants designated below was added to individual emulsion dispersions. 1.5 cc. of 10% saponin and 1.5 cc. of 10% Alkagel (trade name of Amalgamated Chemical Corp, Philadelphia, Pennsylvania, for a sodium amide sulfonate) were then added to each dispersion. The dispersion was stirred for 5 minutes at 38 C. and coated on a subcoated cellulose acetate film base.
  • the film unit was then exposed in a standard sensitometer and developed for 1% minutes in Dektol (trade name of Eastman Kodak Company, Rochester, N.Y., for a photographic developing solution).
  • Example 2 The procedure of Example 1 was repeated with the exception that the film unit was stored for 1 week at a temperature of 120 F. prior to exposure and development.
  • Example 3 The procedure of Example 1 was repeated with the exception that the dispersion was coated on the exposed surface of a dye-containing layer prepared by coating a subcoated cellulose acetate film base coated with sufficient 2- (p- [2,5 '-dihydroxyphenethyl] -phenylazo -4-isopropoxy-l-naphthol, dispersed in a 4% solution of gelatin, to give a coverage of 100 to 110 mgs. per square foot.
  • Example 4 The procedure of Example 3 was repeated with the exception that the film unit was stored for 1 week at a temperature of 120 F. prior to exposure in the sensitometer and development.
  • Example 5 The procedure of Example 3 was repeated with the exception that 2 mgs. of l,1'-diethyl-3,3-bis-(fl-carboxyethyl) 5,5-dichloro-benzimidazolecarbocyanine betaine was included in the silver iodobromide dispersion.
  • Example 6 The procedure of Example 5 was repeated with the exception that the film unit was subjected to storage for 1 week at a temperature of 120 F. prior to exposure and development.
  • Spe- Dye developers are compounds which contain, in the same molecule, both the chromophoric system of a dye and also a silver halide developing function.
  • a silver halide developing function is meant a grouping adapted to develop exposed silver halide.
  • a preferred silver halide development function is a hydroquinonyl group.
  • Other suitable developing functions include ortho-dihydroxyphenyl and orthoand para-amino substituted hydroxyphenyl groups.
  • the development function includes a benzenoid developing function, that is, an aromatic developing group which forms qinonoid or quinone substances when oxidized.
  • the preferred dye developers comprise monoazo and anthraquinone dyes which possess one or two hydroquinonyl groups attached to the dyes auxochromophoric system by means of a conjugation interrupting divalent group such as, for example, an alkylene group.
  • a latent image contained in an exposed photosensitive silver halide emulsion is developed and almost concurrently therewith a soluble silver complex is obtained by reaction of a silver halide solvent with the unexposed and undeveloped silver halide of said emulsion.
  • the photosensitive silver halide emulsion is developed with a processing composition in a viscous condition which is spread between the photo sensitive element comprising the silver halide emulsion and a print-receiving element comprising a suitable silver precipitating layer.
  • the processing composition effects development of the latent image in the emulsion and substantially contemporaneous therewith forms a soluble silver complex, for example, a thiosulfate or thiocyanate, with undeveloped silver halide.
  • a soluble silver complex for example, a thiosulfate or thiocyanate
  • This soluble silver complex is, at least in part, transported in the direction of the print-receiving element and the silver thereof is largely precipitated in the silver precipitating layer of said element to form a positive image therein.
  • Additive color reproduction may be produced by exposing a photosensitive silver halide emulsion through an additive color screen having filter media or screen elements each of an individual additive color, such as red or blue or green, and by viewing the reversed or positive silver image, formed by the aforementioned transfer to a transparent print-receiving element, through the same or a similar screen which is suitably registered with the re versed positive image carried by the print-receiving layer.
  • an additive color screen having filter media or screen elements each of an individual additive color, such as red or blue or green
  • a photosenstive element containing a dye developer and a silver halide emulsion is exposed and wetted by a liquid processing composition, for example, by immersion, coating, spraying, flowing, etc., in the dark, and the exposed photosensitive element is superposed prior to, during, or after wetting, on a sheetlike support element which may be utilized as an image-receiving element.
  • the liquid processing composition is applied to the photosensitive element in a substantially uniform layer as the photosensitive ele ment is brought into superposed relationship with the image-receiving layer. The liquid processing composition permeates the emulsion to initiate development.
  • the dye developer is immobilized or precipitated in exposed areas as a consequence of the development.
  • This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation and especially as regards its solubility in alkaline solutions. It may also be due in part to a tanning effect on the emulsion by oxidized developing agent, and in part to a localized exhaustion of alkali as a result of development.
  • the dye developer is unreacted and diffusible and thus provides an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition, as a function of the point-to-point degree of exposure of the silver halide emulsion.
  • the layer of liquid processing composition may be utilized as the image-receiving layer.
  • the image-receiving element receives a depthwise diffusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide the reversed or positive color image of the developed image.
  • the image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. If the color of the transferred dye developer is affected by changes in the pH of the image-receiving element, this pH may be adjusted to provide a pH affording the desired color.
  • the desired positive image is revealed by stripping the image-receiving layer from the photosensitive element at the end of a suitable imbibition period.
  • Multicolor images may be obtained using color imageforming components such as, for example, the previously mentioned dye developers, in diffusion transfer processes by several techniques.
  • One such technique contemplates the use of a photosensitive silver halide stratum comprising at least two sets of selectively sensitizied minute photosensitive elements arranged in the form of a photosensitive screen. Transfer processes of this type are disclosed in the previously noted US. Patent No. 2,983,606.
  • each of the minute photosensitive elements has associated therewith an appropriate dye developer in or behind the silver halide emulsion portion.
  • a suitable photosensitive screen prepared in accordance with the disclosures of said patent, comprises minute red-sensitized emulsion elements, minute greensensitized emulsion elements and minute blue-sensitized emulsion elements arranged in side-by-side relationship in a screen pattern and having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • Another process for obtaining multicolor transfer images utilizing dye developers employs an integral multilayer photosensitve element, such as is disclosed in the aforementioned copending US. application of Edwin H. Land and Howard G. Rogers, Ser. No. 565,135, filed Feb. 13, 1956, wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed, simultaneously and without'separation, with a single, common image-receiving layer.
  • a suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • the dye developer may be utilized in the silver halide emulsion layer, for example, in the form of particles, or it may be employed as a layer behind the appropriate silver halide emulsion strata.
  • each set of silver halide emulsion and associated-dye developer strata may be separated from other sets by suitable interlayers, for example, by a layer of gelatin or polyvinyl alcohol.
  • suitable interlayers for example, by a layer of gelatin or polyvinyl alcohol.
  • ayellow dye developer of the appropriate spectral characteristics and present in a state capable of functioning as a yellow filter may be employed. In such instances, a separate yellow filter may be omitted.
  • a photosensitive element was prepared by coating a gelatin-coated film base with s-uflicient 2-(p-[2,5-dihydroxyphenethyl]- phenylazo)-4-isopropoxy-l-naphthol, dispersed in a 4% solution of gelatin, to give a coverage of to mgs. per square foot.
  • a silver iodobromide emulsion prepared according to the procedure of Example 1 and containing 12% silver in a 9% solution of gelatin and 1,1'-diethyl-3,3-bis-(fl-carboxyethyl -5 ,5 '-dichloro-benzimidazolecarbocyanine betaine was applied.
  • the photosensitive elements were then exposed and processed by spreading the aqueous liquid processing composition comprising:
  • an image-receiving element comprising a sheet of cellulose acetate s-ubcoated baryta paper having coated thereon a mixture of polyvinyl alcohol and poly-4-vinylpyridine, as said elements were brought into superposed relationship. After an imbibition period of one minute, the image-receiving element was separated and revealed a monochromatic reversed magenta dye image of the photosensitive elements exposure response.
  • the photosensitive elements comprised a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a bluesensitive silver halide emulsion stratum; said emulsions having dispersed in water-immiscible organic solvents and contained in separate alkali-permeable gelatin layers behind them, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • the particular dye developers employed in the photosensitive elements were 1,4-bis-(a-methyl-fi-hydroquinonylethylamino)-5,8- dihydroxyanthraquinone (a cyan dye developer); 2-(p- [2,5'-dihydroxyphenethyl] phenylazo)-4-isopropoxy-1- naphthol a magenta dye developer); and 1-phenyl-3-nhexyl-carbxamido-4-(p-[hydroquinonylethyl] phenylazo)-5-pyrazolone (a yellow dye developer).
  • the lastmentioned cyan dye developer is disclosed in the copending U.S. application of Blout et al. Ser. No. 233,461, filed Oct. 26, 1962, and the last-mentioned yellow and magenta dye developers are disclosed in the copending US. application of Blout et al. Ser. No. 145,978, filed Oct. 18, 1961.
  • a further technique for obtaining multicolor images employs a plurality of photosensitive elements associated with an appropriate number of image-receiving elements and adapted to be treated with one or more liquid processing compositions, the appropriate dye developers being incorporated in the photosensitized elements.
  • Examples of fil-m processes of this type are disclosed in US. Patent No. 2,647,049, issued July 28, 1953.
  • the preceding color image-forming components are preferably selected for their ability to provide colors that are useful in carrying out subtractive color photography, i.e., cyan, magenta and yellow. It should be noted that it is within the scope of this invention to use mixtures of dye developers, for example, to obtain a desired color, e.g., black. Thus it is to be understood that the expression color as used herein is intended to include the use of a plurality of colors to obtain black, as well as the use of a single black dye developer.
  • the dye developers employed in the processes of this invention may be incorporated in the photosensitive elements in, on, or behind the respective silver halide emulsion.
  • the dye developer may, for example, be in a coating or layer behind the silver halide emulsion and such a layer of dye developer may be applied by the use of a coating solution containing about 0.5 to 8%, by Weight, of the respective dye developer.
  • the liquid processing composition referred to for effecting monochromatic and multicolor transfer processes comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate and possesses a pH in excess of 12 preferably. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin uniform layer, it includes a viscosityincreasing compound constituting a film-formaing material of the type which, when said composition is spread and dried, forms a relatively firm and relatively stable film.
  • an alkaline compound for example, diethylamine, sodium hydroxide or sodium carbonate
  • a preferred film-forming material is a high molecular weight polymer such as a polymeric, water-soluble ether which is inert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
  • a high molecular weight polymer such as a polymeric, water-soluble ether which is inert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
  • Other film-forming materials or thickening agents whose ability to increase viscosity is substantially unalfected if left in solution for a long period of time may also be used.
  • the film-forming material is preferably contained in the processing composition in suitable quantities to impart to said composition a viscosity in excess of 1,000 centipoises at a temperature of approximately 24 C. and preferably of the order of 1,000 to 200,000 centipoises at said temperature.
  • liquid processing composition employed may contain an auxiliary or accelerating developing agent, such as p-methy-laminophenol, 2,4-diaminophenol, p-benzylaminophenol, hydroquinone, toluhydroquinone, phenylhydroquinone, 4'-methylphenylhydroquinone, etc. It is also contemplated to employ a plurality of auxiliary or accelerating developing agents, such as a 3-pyrazolidone developing agent and a benzenoid developing agent, as disclosed in US. Patent No. 3,039,869, issued June 19, 1962.
  • auxiliary developing agents examples include 1-phenyl-3-pyrazolidone in combination with p-benzylaminophenol and l-phenyl-S-pyrazolidone in combination with 2,5-bis-ethyleneimino-hydroquinone.
  • auxiliary developing agents may be employed in the liquid processing composition or they may be initially incorporated, at least in part, in the silver halide emulsion strata or the strata containing the dye developers.
  • the dye developer oxidized during development may be oxidized and immobilized as a result of a reaction, e.g., an energy-transfer reaction, with the oxidation product of an oxidized auxiliary developing agent, the latter developing agent being oxidized by the development of exposed silverhalide.
  • a reaction e.g., an energy-transfer reaction
  • Such a reaction of oxidized developing agent with unoxidized dye developer would regenerate the auxiliary developing agent for further reaction with the exposed silver halide.
  • Camera apparatus of this type permits successive exposure of individual frames of the photosensitive element, from the emulsion side thereof, as well as individual processing of an exposed frame by bringing said exposed frame into superposed relation with a predetermined portion of the image-receiving element, while drawing these portions of the film assembly between a pair of pressure rollers, and require a container associated there with to effect the spreading of the processing liquid released by rupture of said container, between and in contact with the exposed photosensitive frame and the predetermined registered area of the image-receiving element.
  • the concentration of developing agent may be varied over a wide range and when desirable the developing agent may be disposed in the photosensitive element, prior to the exposure of the emulsion, in a separate permeable layer of the photosensitive element and/ or in the photosensitive emulsion.
  • the support layers referred to may comprise any of the various types of conventional rigid or flexible supports, for example, glass, paper, metal, and polymeric films of both synthetic types and those derived from naturally occurring products.
  • Suitable materials include paper; aluminum; polymethacrylic acid, methyl and ethyl esters; vinyl chloride polymers; polyvinyl acetal; polyamides such as nylon; polyesters such as polymeric films derived from ethylene glycol terephthalic acid; and cellulose derivatives such as cellulose acetate, tria-cetate, nitrate, propionate, butyrate, acetate-propionate, or acetate-butyrate.
  • silver halides of varying halide concentrations may be advantageously employed and that the silver halide emulsions employed may be chemically sensitized by any of the accepted procedures.
  • the emulsions may be chemically sensitized with sulfur compounds such as sodium thiosulfate or thiourea; with reducing substances such as stannous chloride; with salts of noble metals such as gold, rhodium and platinum; with amines and polyamines; with quaternary ammonium compounds such as a-picolinium bromide, etc., and with polyethylene glycols and derivatives of same.
  • the emulsions may also be optically sensitized with cyanine and merocyanine dyes and, where desired, additional antifoggants, restrainers, accelerators, preservatives, and/ or coating aids may be included in the composition of the emulsion.
  • the image-receiving element for use in monochromatic and multichromatic subtractive color processes, comprises an image-receiving layer of opaque or transparent material which is liquid permeable and dyeable from alkaline solutions and which for purposes of simplicity may comprise a single sheet of permeable material, for example, paper.
  • This element may comprise a support upon which at least one liquid-permeable and dyeable layer is mounted.
  • the support layer may have a water-impermeable subcoat over which the stratum of permeable and dyeable material is applied.
  • the dyeable layer may comprise a layer of liquid processing composition which is adapted to remain adhered to the support layer upon stripping.
  • nylon such as N-methoxyrnethyl polyhexamethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; baryta paper, i.e., a support having a baryta coating thereon; cellulose acetate with filler as, for example, one-half cellulose acetate and one-half oleic acid; gelatin; and other materials of a similar nature.
  • Preferred materials comprise polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine, as disclosed in the copending U.S. application of Howard C. Hass, Ser. No. 50,848, filed Aug. 22, 1960.
  • Particularly desired image-receiving elements comprise a flexible laminate which includes, in sequence, a support a polymeric acid layer, an optional permeable polymeric timing layer, and a solution dyeable polymeric imagereceiving layer as disclosed in the copending US. application of Edwin H. Land, Ser. No. 234,864, filed Nov. 1,1962.
  • a rupturable container provides a convenient means for spreading a liquid processing composition between layers of a film unit whereby to permit the processing to be carried out within a camera apparatus
  • a photosensitive element after exposure in suitable apparatus and while preventing further exposure thereafter to actinic light, may be removed from such apparatus and permeated with the liquid processing composition, as by coating the composition on said photosensitive element or otherwise wetting said element with the composition, following which the permeated, exposed photosensitive element, still, without additional exposure to actinic light, is brought. into contact with the imagereceiving element for image formation in the manner heretofore described.
  • the expression positive image has been used. This expression should not be interpreted in a restrictive sense since it is used primarily for purposes. of illustration, in that it defines the image produced on the image-carrying layer as being reversed, in the positive-negative sense, with respect to the image in thephotosensitive element.
  • the expression positive image assume that the photosensitive element is exposed to actinic light through a negative transparency. In this case, the latent image in the photosensitive element will be a positive and the image produced on the image-carrying layer will be a negative.
  • the expression positive image is intended to cover such an image produced on the image-carrying layer.
  • a photographic product which comprises, in combination, a plurality of layers including a support, a silver halide emulsion located in a layer on said support, said silver halide emulsion having associated therewith an antifoggant of the formula:
  • emulsion also having associated therewith, in a layer on the same side of said support, a dye which is a silver halide developing agent.
  • a photographic product as defined in claim 1 wherein said compound is selected from the group consisting of 3-carboxymethyl-2-methy1 benzothiazole, 3-carboxymethyl-2-methyl benzolselenazole, 2-methyl-3-( -sulfopropyl -benzolselenazole, 2-methyl-3-(6-sulfobutyl -benzolselenazole, 3-carboxymethyl-S-chloro-2-methyl-benzothiazole, and 3-(fl-carboxyethyl)-2-methyl-benzoselenazole.
  • a process of forming diffusion transfer images in color which comprises the steps of developing an exposed photosensitive element comprising a plurality of layers including a silver halide emulsion layer, at least one of said layers containing a dye, which dye is a silver halide developing agent, by contacting said element with an aqueous alkaline solution, immobilizing said dye in the exposed areas of said element, as a result of development, forming thereby an imagewise distribution of mobile dye, as a function of the point-to-point degree of exposure of said element, and transferring, by imbibition, at least a portion of said imagewise distribution of mobile dye to a superposed image receiving layer to provide thereto a positive dye image, the improvement which comprises at least one of said plurality of layers including an antifoggant of the formula:
  • a multicolor difiusion transfer process which comprises the steps of developing an exposed photosensitive element comprising a plurality of layers including blue-sensitive, green-sensitive and red-sensitive silver halide gelatin emulsion layers mounted on a common support, said blue-sensitive, green-sensitive and redsensitive silver halide gelatin emulsion layers having positioned contiguous, respectively, yellow, magenta and cyan dyes, each of said yellow, magenta and cyan dyes being a silver halide developing agent, by permeating said photosensitive element with an aqueous alkaline processing composition, immobilizing said yellow, magenta and cyan dyes in exposed areas, as a result of development, forming thereby an imagewise distribution of mobile yellow, magenta and cyan dye, as a function of the point-to-point degree of exposure of said element, and transferring, by imbibition, at least a portion of each of said imagewise distributions of mobile dye to a superposed image-receiving layer to provide thereto a multicolor
  • A represents an acid group selected from the group consisting of carboxylic and sulfonic acid groups
  • n represents a positive integer from 1 to 4, inclusive
  • :R represents a monovalent radical selected from the group consisting of an alkyl group containing from 1 to 4 carbon atoms, a phenyl group, and hydrogen
  • X comprises the nonrnetallic atoms necessary to complete an aromatic ring system of the benzene series
  • Y is selected from the group consisting of oxygen, sulfur and selenium atoms
  • Z represents an anion.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US305857A 1963-08-30 1963-08-30 Photographic products and processes Expired - Lifetime US3326681A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NL127569D NL127569C (en)) 1963-08-30
US305857A US3326681A (en) 1963-08-30 1963-08-30 Photographic products and processes
FR985027A FR1406208A (fr) 1963-08-30 1964-08-12 Nouveaux produits photographiques et leur procédé d'utilisation
NL6409622A NL6409622A (en)) 1963-08-30 1964-08-20
BE652267D BE652267A (en)) 1963-08-30 1964-08-25
DEJ26472A DE1285302B (de) 1963-08-30 1964-08-28 Photographische Silberhalogenidemulsion
GB35394/64A GB1080228A (en) 1963-08-30 1964-08-28 Antifoggants for silver halide materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US305857A US3326681A (en) 1963-08-30 1963-08-30 Photographic products and processes

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US3326681A true US3326681A (en) 1967-06-20

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US305857A Expired - Lifetime US3326681A (en) 1963-08-30 1963-08-30 Photographic products and processes

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US (1) US3326681A (en))
BE (1) BE652267A (en))
DE (1) DE1285302B (en))
GB (1) GB1080228A (en))
NL (2) NL6409622A (en))

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50137736A (en)) * 1974-04-19 1975-11-01
US3954478A (en) * 1973-12-21 1976-05-04 Fuji Photo Film Co., Ltd. Silver halide emulsion containing an alkenyl benzothiazolium salt as stabilizer
US5149619A (en) * 1988-11-15 1992-09-22 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5620837A (en) * 1995-12-28 1997-04-15 Eastman Kodak Company Color photographic element containing benzazolium compounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131038A (en) * 1932-05-26 1938-09-27 Eastman Kodak Co Photographic emulsion containing alkyl quaternary salts of thiazoles and the like asantifoggants
GB587434A (en) * 1939-12-20 1947-04-25 Gevaert Photo Prod Nv Improvements in and relating to the preparation of heterocyclic nitrogen compounds
US2912329A (en) * 1957-08-23 1959-11-10 Eastman Kodak Co Green sensitization for photographic emulsions containing coupler dispersions
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US3189453A (en) * 1961-08-25 1965-06-15 Eastman Kodak Co Photographic emulsions containing thio derivatives as fixers and method of using same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE704141C (de) * 1938-03-08 1941-03-24 I G Farbenindustrie Akt Ges Verfahren zur Sensibilisierung von Halogensilberemulsionen
BE484580A (en)) * 1947-08-29
DE929080C (de) * 1951-10-23 1955-08-16 Agfa Ag Fuer Photofabrikation Verfahren zur Herstellung von Betain-Cyanin-Farbstoffen und von Betain-Styryl-Farbstoffen
BE566164A (en)) * 1957-03-28
BE566601A (en)) * 1957-04-11
BE570362A (en)) * 1957-08-16
DE1063028B (de) * 1957-09-10 1959-08-06 Wolfen Filmfab Veb Verfahren zur Sensibilisierung von Halogensilberemulsionen
NL246035A (en)) * 1958-12-04

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131038A (en) * 1932-05-26 1938-09-27 Eastman Kodak Co Photographic emulsion containing alkyl quaternary salts of thiazoles and the like asantifoggants
GB587434A (en) * 1939-12-20 1947-04-25 Gevaert Photo Prod Nv Improvements in and relating to the preparation of heterocyclic nitrogen compounds
US2912329A (en) * 1957-08-23 1959-11-10 Eastman Kodak Co Green sensitization for photographic emulsions containing coupler dispersions
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color
US3189453A (en) * 1961-08-25 1965-06-15 Eastman Kodak Co Photographic emulsions containing thio derivatives as fixers and method of using same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954478A (en) * 1973-12-21 1976-05-04 Fuji Photo Film Co., Ltd. Silver halide emulsion containing an alkenyl benzothiazolium salt as stabilizer
JPS50137736A (en)) * 1974-04-19 1975-11-01
US5149619A (en) * 1988-11-15 1992-09-22 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5620837A (en) * 1995-12-28 1997-04-15 Eastman Kodak Company Color photographic element containing benzazolium compounds

Also Published As

Publication number Publication date
DE1285302B (de) 1968-12-12
NL127569C (en))
BE652267A (en)) 1965-02-25
NL6409622A (en)) 1965-03-01
GB1080228A (en) 1967-08-23

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