EP0346071A2 - Photographic process - Google Patents
Photographic process Download PDFInfo
- Publication number
- EP0346071A2 EP0346071A2 EP89305696A EP89305696A EP0346071A2 EP 0346071 A2 EP0346071 A2 EP 0346071A2 EP 89305696 A EP89305696 A EP 89305696A EP 89305696 A EP89305696 A EP 89305696A EP 0346071 A2 EP0346071 A2 EP 0346071A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- dye
- substituted
- unsubstituted
- independently
- solubilizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- G03C1/005—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
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C1/12—Methine and polymethine dyes
- G03C1/14—Methine and polymethine dyes with an odd number of CH groups
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
Definitions
- This invention relates to photography, especially photographic processes for elements having silver halide sensitized with a cyanine dye.
- Silver halide elements are usually subjected to some type of photographic processing after exposure in order to form images suitable for viewing.
- the processing generally involves contacting the element with a developer solution to cause formation of a silver image corresponding to a latent image formed on the silver halide during exposure, and then with a fixing solution to solubilize and remove silver halide that was not converted to silver during development.
- a developer solution to cause formation of a silver image corresponding to a latent image formed on the silver halide during exposure
- a fixing solution to solubilize and remove silver halide that was not converted to silver during development.
- Any of a number of other known processing solutions may also be used, such as stop baths to halt image development, bleach solutions to remove already formed silver from the element, and a number of other known solutions (e.g., stabilizer baths, hardener solutions, wash baths, and the like).
- the silver halide that is used in photographic elements is usually inherently sensitive only to blue light. It is therefore often desirable, in order to provide sensitivity to light of other regions of the spectrum or to enhance the sensitivity to blue light, to spectrally sensitize the silver halide by adsorbing a sensitizing dye to the silver halide, thus imparting to the silver halide sensitivity to the wavelength of light absorbed by the dye.
- the sensitizing dye can come out of the element and enter one or more of the processing solutions. Indeed, it is usually desirable to remove (usually in the fixing bath)the sensitizing dye from the element during processing so as to minimize adverse effects on image quality that can occur as a result of sensitizing dye remaining in the element after processing.
- sensitizing dye instead of coming out of the element and dissolving in a processing solution, is removed from the element, but is not fully solubilized in the processing solution and forms solid particles. These particles can have a number of adverse effects. They can adhere to the surface of the element, forming visible specks or blotches on the image. They can also adhere to processing equipment, impeding flow or mixing of processing solutions, and necessitating costly and time-consuming cleaning procedures.
- R5 and R6 are each independently hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, with the proviso that the dye solubilizing compound comprises at least four solubilizing groups as substituents on R5's or R6's that are alkyl or aryl wherein at least one of the solubilizing groups is anionic sulfo.
- R1, R2, R3, and R4 are each independently halogen (e.g. fluoro, chloro, bromo, iodo), substituted or unsubstituted alkoxy of from 1 to 6 carbon atoms (e.g., methoxy, ethoxy, propoxy).
- R5 end R6 are each independently hydrogen, substituted or unsubstituted alkyl of from 1 to 7 carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, t -butyl, n-hexyl, etc.), or substituted or unsubstituted aryl (e.g., phenyl, naphthyl, and the like).
- Useful substituents for the above R groups can include any of a number substituents commonly utilized for such groups that do not adversely affect the properties of the compound to a significant degree. Examples of such substituents include halogen, alkyl, aryl, and alkoxy as described above, as well as other known substituents, such as allyl, thioethers, etc. . . .
- solubilizing groups are groups that tend to increase the solubility of organic compounds in water.
- solubilizing groups are well-known in the art and include, for example, sulfo, carboxy, and hydroxy.
- anionic sulfo is meant an ionized SO group associated with a counterion, as opposed to an acidic -SO3H group.
- the sulfo group may be in acid form prior to such contact.
- the solubilizing compound of formula (I) is being used in conjunction with a developer solution with a high pH (usually 9 or above), then the solubilizing group may be an acidic -SO3H group until contact with the developing solution, at which time the high pH would ionize the sulfo group.
- solubilizing groups include any group whose presence as a substituent on the compound of formula (I) will tend to render it more soluble in aqueous solutions than without it.
- the compounds of formula (I) can be made by methods well-known in the art. Such methods are described in, for example, U.S. Patents 3,617,295, 3,615,641, 2,937,089, and 3,615,632.
- the dye solubilizing compound of formula (I) can be incorporated in any processing solution where the sensitizing dye would be present in the solution at a concentration sufficient to cause formation of solid dye particles in the absence of the dye solubilizing compound.
- the dye solubilizing compound can be incorporated in the photographic element so that the dye solubilizing compound is present when the element is contacted with the solution that is susceptible to dye particle formation.
- the compound of formula (I) can be used in conjunction with any combination of photographic element and process that is susceptible to formation of solid particles of cyanine sensitizing dye in any of the processing solutions.
- the cyanine sensitizing dye can be any of a number of such dyes, which are well-known in the art.
- the cyanine spectral sensitizing dyes include, joined by a methine linkage, two basic heterocyclic nuclei, such as those derived from quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz[e]indolium, oxazolium, thiazolium, selenazolinium, imidazolium, benzoxazolinium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, thiazolinium dihydronaphthothiazolium, pyrylium, and imidazopyrazinium quaternary salts. Further description and examples of such dyes can be found in James, The Theory of the Photographic Process 4th ,
- Useful cyanine dyes include those according to the formula:
- Z1 and Z2 represent the atoms necessary to complete a substituted or unsubstituted aromatic ring structure.
- R7 and R8 are each independently substituted or unsubstituted alkyl of 1 to 12 carbon atoms (e.g., methyl, ethyl, propyl, butyl). R7 and R8 may be substituted with substituents as is known in the art, such as halogen, alkoxy, aryl, aryloxy, sulfo, carboxyl, and the like).
- L1, L2, and L3 are each independently substituted (with substituents known in the art, e.g., alkyl) or unsubstituted methine linkages.
- X is O, S, Se, -C-, or N- and n is 0, 1, or 2.
- Photographic elements useful in the practice of the invention generally comprise a support having thereon at least one silver halide emulsion layer.
- the silver halide emulsion can comprise any type of silver halide that is useful in photographic emulsions. This includes silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, or mixtures thereof.
- the silver halide can be in the form of grains bounded by 100, 111, or 110 crystal planes, as described in Research Disclosure I , or in the form of tabular grains, as described in Research Disclosure , January, 1983, item 22534.
- the silver halide can be present in any amount known in the art to be useful in photographic emulsions.
- the silver halide is generally present in the emulsion in an amount such that when it is coated as a layer in a photographic element, the coverage of silver will be from 1.1 to 3.2 g/m2.
- the amount of sensitizing dye in the emulsion can be any amount that is known in the art to be useful for spectral sensitization of silver halide, subject to the requirement that it be sufficient to cause formation of solid dye particles in a solution for processing the element.
- the quantity of dye employed will vary with the specific dye or dye combination chosen as well as the size and aspect ration of the grains. It is known in the photographic art that optimum spectral sensitization is generally obtained with organic dyes at 25 to 100 percent of monolayer coverage of the total available surface area of surface sensitive silver halide grains, as disclosed for example, in West et al, "The Adsorption of Sensitizing Dyes in Photographic Emulsions," Journal of Phys. Chem. , Vol. 56, p.
- Optimum dye concentration levels can be chosen by procedures taught by Mees, Theory of the Photographic Process , Macmillan (1942), pp. 1067-69.
- Preferred dye amounts in photographic elements useful according to the present invention range from 1.1 to 10.8 g/m2.
- One or more spectral sensitizing dyes may be used to achieve a desired spectral sensitization of the silver halide as well as to achieve results such as supersensitization, as discussed by Gilman in Photographic Science and Engineering , Vol. 18, 1974, pp. 418-30.
- supersensitizing dye combinations include those disclosed in Mcfall et al U.S. Patent 2,933,390, Jones et al U.S. Patent 2,937,089, Motter U.S. Patent 3,506,443, and Schwan et al U.S. Patent 3,672,898.
- the emulsion preferably includes a vehicle for coating the emulsion as a layer of a photographic element.
- vehicle include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives (e.g., cellulose esters), gelatin (e.g., alkali-treated gelatin such as cattle bone or hide gelatin, or acid-treated gelatin such as pigskin gelatin), gelatin derivatives (e.g., acetylated gelatin, phthalated gelatin, and the like), polysaccharides (e.g., dextran, gum arabic, casein, pectin, and the like), and others, as described in Research Disclosure I .
- Also useful as vehicles or vehicle extenders are hydrophilic water-permeable colloids.
- polystyrene resin examples include synthetic polymeric peptizers, carriers, and/or binders such as poly(vinyl alcohol), poly(vinyl lactams), acrylamide polymers, polyvinyl acetals, polymers of alkyl and sulfoalkyl acrylates and methacrylates, hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine, methacrylamide copolymers, and the like, as described in Research Disclosure I .
- the vehicle can be present in the emulsion in any amount known to be useful in photographic emulsions.
- the silver halide emulsion can also include any of the addenda known to be useful in photographic emulsions. These include chemical sensitizers, such as active gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, phosphorous, or combinations thereof. Chemical sensitization is generally carried out at pAg levels of from 5 to 10, pH levels of from 5 to 8, and temperatures of from 30 to 80°C, as illustrated in Research Disclosure , June, 1975, item 13452 and U.S. Patent 3,772,031.
- chemical sensitizers such as active gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, phosphorous, or combinations thereof. Chemical sensitization is generally carried out at pAg levels of from 5 to 10, pH levels of from 5 to 8, and temperatures of from 30 to 80°C, as illustrated in Research Disclosure , June, 1975, item 13452
- addenda include brighteners, antifoggants, stabilizers, filter dyes, light absorbing or reflecting pigments, vehicle hardeners such as gelatin hardeners, coating aids, dye-forming couplers, and development modifiers such as development inhibitor releasing couplers and bleach accelerators.
- the emulsion and other layers of photographic elements can be coated onto a support using techniques well-known in the art. These techniques include immersion or dip coating, roller coating, reverse roll coating, air knife coating, doctor blade coating, stretch-flow coating, and curtain coating.
- the silver halide emulsion layer of the photographic element can be coated simultaneously or sequentially with other emulsion layers, subbing layers, filter dye layers, or interlayers or overcoat layers containing various addenda known to be included in photographic elements, such as antifoggants, oxidized developer scavengers, DIR couplers, antistatic agents, optical brighteners, light-absorbing or light-scattering pigments, and the like.
- the coated layers of the photographic element may be chill-set or dried, or both. Drying may be accelerated by known techniques such as conduction, convection, radiation heating, or a combination thereof.
- the photographic element useful in the practice of the invention can be black and white or color.
- Certain black and white elements requiring moderately high density in imaged areas, minimum density in non-imaged areas, and sufficient contrast to yield high quality definition images e.g., microfilm or microfiche elements
- contain sufficient amounts of silver halide i.e., 1.1 to 2.2 g/m2 so that when they are sensitized with a cyanine dye, the amount of cyanine dye is sufficient to cause dye particle formation in processing solutions.
- a color photographic element generally contains three silver halide emulsion layers: a blue-sensitive layer having a yellow color coupler associated therewith, a green-sensitive layer having a magenta color coupler associated therewith, and a red-sensitive layer having a cyan color coupler associated therewith.
- the compound of formula (I) can be used in conjunction with essentially any known process, the exact type of which is not critical. Such processes generally include contacting the element with an aqueous alkaline solution of a developing agent, and then contacting the element with a solution of fixing agent or with bleaching and fixing agent(s). Examples of processing formulations and techniques are described in L. Mason, Photographic Processing Chemistry , Focal Press, London, 1966; Processing Chemicals and Formulas , Publication J-1, Eastman Kodak Company, 1985; Photo-Lab Index , Morgan & Morgan, Inc., Dobbs Ferry, New York, 1977; and Neblette's Handbook of Photography and Reprography Materials, Processes and Systems , VanNostrand Reinhold Co., 7th Ed., 1977.
- the compound of formula (I) can be incorporated in the element or in any processing solution in which solid dye particle formation is a problem.
- the compound is to be included in a processing solution, it is preferably incorporated in a developing solution or a fixing solution.
- Developing solutions generally have a pH of 9 or more, although that is not a requirement of the invention.
- the use of the compound of formula (I) in an alkaline developing solution, as indicated above, does allow for ionization of any acidic sulfo solubilizing groups on the compound.
- the developing agent can be any of the known developing agents, as described in James, The Theory of the Photographic Process , 4th, Macmillan, 1977 [hereinafter "James"], Chapter 11.
- Useful developing agents include hydroquinones, catechols, aminophenols, pyrazolidones, phenylenediamines, tetrahydroquinolines, bis(pyridone)amines, cycloalkenones, pyramidines, reductones, and coumarins.
- Fixing agents are also known in the art, as described in James, Chapter 15.
- Useful fixing agents include thiosulfates, thiocyanates, cyanides, sulfite, ammonia, thiourea, thioacids, thiosugars, concentrated alkali halides, and organic solvents such as acetone.
- Thiosulfates, such as sodium thiosulfate or ammonium thiosulfate are among the most commonly-used fixing agents.
- wash baths consisting primarily of water and optionally pH buffers or other stabilizers, bleach or bleach/fix solutions, color developer solutions (which may or may not contain photographic couplers, stop baths for arresting photographic development, gelatin hardening solutions, and other known photographic processing solutions. All these solutions and processing steps are well-known in the art.
- a photographic element was prepared, having an emulsion layer containing gelatin at a coverage of 1.56 g/m2 and silver bromide at a coverage of 1.61 g/m2 sensitized with a dye of the formula: at a coverage of 5.4 mg/m2. Samples of the element were processed in a semicontinuous batch process in which the element moves successively from one tank to the next of well-mixed non-replenished processing solutions.
- tanks 1 and 2 also contained 0.5 g/l of compound 5 from Table I. After 18.6 m2 of film had been processed, no dye particles were observed in any of the tanks.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
- This invention relates to photography, especially photographic processes for elements having silver halide sensitized with a cyanine dye.
- Silver halide elements are usually subjected to some type of photographic processing after exposure in order to form images suitable for viewing. The processing generally involves contacting the element with a developer solution to cause formation of a silver image corresponding to a latent image formed on the silver halide during exposure, and then with a fixing solution to solubilize and remove silver halide that was not converted to silver during development. Any of a number of other known processing solutions may also be used, such as stop baths to halt image development, bleach solutions to remove already formed silver from the element, and a number of other known solutions (e.g., stabilizer baths, hardener solutions, wash baths, and the like).
- The silver halide that is used in photographic elements is usually inherently sensitive only to blue light. It is therefore often desirable, in order to provide sensitivity to light of other regions of the spectrum or to enhance the sensitivity to blue light, to spectrally sensitize the silver halide by adsorbing a sensitizing dye to the silver halide, thus imparting to the silver halide sensitivity to the wavelength of light absorbed by the dye.
- When photographic elements having spectrally sensitized silver halide are processed, the sensitizing dye can come out of the element and enter one or more of the processing solutions. Indeed, it is usually desirable to remove (usually in the fixing bath)the sensitizing dye from the element during processing so as to minimize adverse effects on image quality that can occur as a result of sensitizing dye remaining in the element after processing.
- It has now been found, however, that certain problems are encountered in situations where a large amount of sensitizing dye is present in a photographic element (e.g., at a level of 3.3 mg/m²), or when the rate of replenishment of the processing solution(s) is low, or both. Large amounts of sensitizing dye may be present because of the particular sensitization of silver halide that is desired, or simply because an element contains a large amount of silver halide. In such situations, the sensitizing dye, instead of coming out of the element and dissolving in a processing solution, is removed from the element, but is not fully solubilized in the processing solution and forms solid particles. These particles can have a number of adverse effects. They can adhere to the surface of the element, forming visible specks or blotches on the image. They can also adhere to processing equipment, impeding flow or mixing of processing solutions, and necessitating costly and time-consuming cleaning procedures.
- It has now been found that the formation of solid dye particles in processing solutions can be reduced by a process where the the element is contacted with a processing solution that is susceptible to dye particle formation in the presence of an effective amount of a dye solubilizing compound of the formula:
- R₅ and R₆ are each independently hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, with the proviso that the dye solubilizing compound comprises at least four solubilizing groups as substituents on R₅'s or R₆'s that are alkyl or aryl wherein at least one of the solubilizing groups is anionic sulfo.
- According to formula (I), R₁, R₂, R₃, and R₄ are each independently
- For a compound of formula (I) to be useful according to the invention, it must have at least four solubilizing groups as substituents on R₅'s or R₆'s and at least one of those solubilizing groups must be anionic sulfo. These solubilizing groups are groups that tend to increase the solubility of organic compounds in water. Such solubilizing groups are well-known in the art and include, for example, sulfo, carboxy, and hydroxy. By anionic sulfo is meant an ionized SO group associated with a counterion, as opposed to an acidic -SO₃H group. It should be noted that since the invention requires contact of the photographic element in the presence of a compound of formula (I), the sulfo group may be in acid form prior to such contact. For example, if the dye solubilizing compound of formula (I) is being used in conjunction with a developer solution with a high pH (usually 9 or above), then the solubilizing group may be an acidic -SO₃H group until contact with the developing solution, at which time the high pH would ionize the sulfo group.
- Clearly, by inference from the requirement that the compound of formula (I) comprise four solubilizing groups as substituents on R₅'s or R₆'s, at least two of R₁, R₂, R₃, or R₄ must be
-
- The compounds of formula (I) can be made by methods well-known in the art. Such methods are described in, for example, U.S. Patents 3,617,295, 3,615,641, 2,937,089, and 3,615,632.
- The dye solubilizing compound of formula (I) can be incorporated in any processing solution where the sensitizing dye would be present in the solution at a concentration sufficient to cause formation of solid dye particles in the absence of the dye solubilizing compound. Alternatively, the dye solubilizing compound can be incorporated in the photographic element so that the dye solubilizing compound is present when the element is contacted with the solution that is susceptible to dye particle formation.
- The compound of formula (I) can be used in conjunction with any combination of photographic element and process that is susceptible to formation of solid particles of cyanine sensitizing dye in any of the processing solutions.
- The cyanine sensitizing dye can be any of a number of such dyes, which are well-known in the art. The cyanine spectral sensitizing dyes include, joined by a methine linkage, two basic heterocyclic nuclei, such as those derived from quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz[e]indolium, oxazolium, thiazolium, selenazolinium, imidazolium, benzoxazolinium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, thiazolinium dihydronaphthothiazolium, pyrylium, and imidazopyrazinium quaternary salts. Further description and examples of such dyes can be found in James, The Theory of the Photographic Process 4th, 1977 and in Research Disclosure, December, 1978, item 17643 (hereinafter referred to as "Research Disclosure I").
-
- In this formula, Z₁ and Z₂ represent the atoms necessary to complete a substituted or unsubstituted aromatic ring structure. R₇ and R₈ are each independently substituted or unsubstituted alkyl of 1 to 12 carbon atoms (e.g., methyl, ethyl, propyl, butyl). R₇ and R₈ may be substituted with substituents as is known in the art, such as halogen, alkoxy, aryl, aryloxy, sulfo, carboxyl, and the like). L₁, L₂, and L₃ are each independently substituted (with substituents known in the art, e.g., alkyl) or unsubstituted methine linkages. X is O, S, Se, -C-, or N- and n is 0, 1, or 2.
- Photographic elements useful in the practice of the invention generally comprise a support having thereon at least one silver halide emulsion layer. The silver halide emulsion can comprise any type of silver halide that is useful in photographic emulsions. This includes silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, or mixtures thereof. The silver halide can be in the form of grains bounded by 100, 111, or 110 crystal planes, as described in Research Disclosure I, or in the form of tabular grains, as described in Research Disclosure, January, 1983, item 22534. The silver halide can be present in any amount known in the art to be useful in photographic emulsions. The silver halide is generally present in the emulsion in an amount such that when it is coated as a layer in a photographic element, the coverage of silver will be from 1.1 to 3.2 g/m².
- The amount of sensitizing dye in the emulsion can be any amount that is known in the art to be useful for spectral sensitization of silver halide, subject to the requirement that it be sufficient to cause formation of solid dye particles in a solution for processing the element. The quantity of dye employed will vary with the specific dye or dye combination chosen as well as the size and aspect ration of the grains. It is known in the photographic art that optimum spectral sensitization is generally obtained with organic dyes at 25 to 100 percent of monolayer coverage of the total available surface area of surface sensitive silver halide grains, as disclosed for example, in West et al, "The Adsorption of Sensitizing Dyes in Photographic Emulsions," Journal of Phys. Chem., Vol. 56, p. 1065, 1952 and Gilman et al U.S. Patent 3,979,213. Optimum dye concentration levels can be chosen by procedures taught by Mees, Theory of the Photographic Process, Macmillan (1942), pp. 1067-69. Preferred dye amounts in photographic elements useful according to the present invention range from 1.1 to 10.8 g/m².
- One or more spectral sensitizing dyes may be used to achieve a desired spectral sensitization of the silver halide as well as to achieve results such as supersensitization, as discussed by Gilman in Photographic Science and Engineering, Vol. 18, 1974, pp. 418-30. Examples of supersensitizing dye combinations include those disclosed in Mcfall et al U.S. Patent 2,933,390, Jones et al U.S. Patent 2,937,089, Motter U.S. Patent 3,506,443, and Schwan et al U.S. Patent 3,672,898.
- The emulsion preferably includes a vehicle for coating the emulsion as a layer of a photographic element. Useful vehicles include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives (e.g., cellulose esters), gelatin (e.g., alkali-treated gelatin such as cattle bone or hide gelatin, or acid-treated gelatin such as pigskin gelatin), gelatin derivatives (e.g., acetylated gelatin, phthalated gelatin, and the like), polysaccharides (e.g., dextran, gum arabic, casein, pectin, and the like), and others, as described in Research Disclosure I. Also useful as vehicles or vehicle extenders are hydrophilic water-permeable colloids. These include synthetic polymeric peptizers, carriers, and/or binders such as poly(vinyl alcohol), poly(vinyl lactams), acrylamide polymers, polyvinyl acetals, polymers of alkyl and sulfoalkyl acrylates and methacrylates, hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine, methacrylamide copolymers, and the like, as described in Research Disclosure I. The vehicle can be present in the emulsion in any amount known to be useful in photographic emulsions.
- The silver halide emulsion can also include any of the addenda known to be useful in photographic emulsions. These include chemical sensitizers, such as active gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, phosphorous, or combinations thereof. Chemical sensitization is generally carried out at pAg levels of from 5 to 10, pH levels of from 5 to 8, and temperatures of from 30 to 80°C, as illustrated in Research Disclosure, June, 1975, item 13452 and U.S. Patent 3,772,031.
- Other addenda include brighteners, antifoggants, stabilizers, filter dyes, light absorbing or reflecting pigments, vehicle hardeners such as gelatin hardeners, coating aids, dye-forming couplers, and development modifiers such as development inhibitor releasing couplers and bleach accelerators. These addenda and methods of inclusion in the emulsion are well-known in the art and are disclosed in Research Disclosure I and the references cited therein.
- The emulsion and other layers of photographic elements can be coated onto a support using techniques well-known in the art. These techniques include immersion or dip coating, roller coating, reverse roll coating, air knife coating, doctor blade coating, stretch-flow coating, and curtain coating.
- The silver halide emulsion layer of the photographic element can be coated simultaneously or sequentially with other emulsion layers, subbing layers, filter dye layers, or interlayers or overcoat layers containing various addenda known to be included in photographic elements, such as antifoggants, oxidized developer scavengers, DIR couplers, antistatic agents, optical brighteners, light-absorbing or light-scattering pigments, and the like. The coated layers of the photographic element may be chill-set or dried, or both. Drying may be accelerated by known techniques such as conduction, convection, radiation heating, or a combination thereof.
- The photographic element useful in the practice of the invention can be black and white or color. Certain black and white elements requiring moderately high density in imaged areas, minimum density in non-imaged areas, and sufficient contrast to yield high quality definition images (e.g., microfilm or microfiche elements), contain sufficient amounts of silver halide (i.e., 1.1 to 2.2 g/m²) so that when they are sensitized with a cyanine dye, the amount of cyanine dye is sufficient to cause dye particle formation in processing solutions. A color photographic element generally contains three silver halide emulsion layers: a blue-sensitive layer having a yellow color coupler associated therewith, a green-sensitive layer having a magenta color coupler associated therewith, and a red-sensitive layer having a cyan color coupler associated therewith.
- The compound of formula (I) can be used in conjunction with essentially any known process, the exact type of which is not critical. Such processes generally include contacting the element with an aqueous alkaline solution of a developing agent, and then contacting the element with a solution of fixing agent or with bleaching and fixing agent(s). Examples of processing formulations and techniques are described in L. Mason, Photographic Processing Chemistry, Focal Press, London, 1966; Processing Chemicals and Formulas, Publication J-1, Eastman Kodak Company, 1985; Photo-Lab Index, Morgan & Morgan, Inc., Dobbs Ferry, New York, 1977; and Neblette's Handbook of Photography and Reprography Materials, Processes and Systems, VanNostrand Reinhold Co., 7th Ed., 1977.
- The compound of formula (I) can be incorporated in the element or in any processing solution in which solid dye particle formation is a problem. When the compound is to be included in a processing solution, it is preferably incorporated in a developing solution or a fixing solution.
- Developing solutions generally have a pH of 9 or more, although that is not a requirement of the invention. The use of the compound of formula (I) in an alkaline developing solution, as indicated above, does allow for ionization of any acidic sulfo solubilizing groups on the compound. The developing agent can be any of the known developing agents, as described in James, The Theory of the Photographic Process, 4th, Macmillan, 1977 [hereinafter "James"], Chapter 11. Useful developing agents include hydroquinones, catechols, aminophenols, pyrazolidones, phenylenediamines, tetrahydroquinolines, bis(pyridone)amines, cycloalkenones, pyramidines, reductones, and coumarins.
- Fixing agents are also known in the art, as described in James, Chapter 15. Useful fixing agents include thiosulfates, thiocyanates, cyanides, sulfite, ammonia, thiourea, thioacids, thiosugars, concentrated alkali halides, and organic solvents such as acetone. Thiosulfates, such as sodium thiosulfate or ammonium thiosulfate are among the most commonly-used fixing agents.
- Other solutions commonly used in the processing of photographic elements, which may also include a compound of formula (I), include wash baths consisting primarily of water and optionally pH buffers or other stabilizers, bleach or bleach/fix solutions, color developer solutions (which may or may not contain photographic couplers, stop baths for arresting photographic development, gelatin hardening solutions, and other known photographic processing solutions. All these solutions and processing steps are well-known in the art.
- The invention is further illustrated by the following examples.
- A photographic element was prepared, having an emulsion layer containing gelatin at a coverage of 1.56 g/m² and silver bromide at a coverage of 1.61 g/m² sensitized with a dye of the formula:
Table II Tank Components (level-g/l) Volume (gal) Processing Time 1 Developer hydroquinone (45) 0.5 15 sec momomethyl-p-amino-phenolsulfonate (12.5) NaSO₃ (140) NaBr (2.5) pH = 10.9 2 same as 1 0.5 15 sec 3 Fixer ammonium thiosulfate (140) 0.5 15 sec NaSO₃ (25) pH = 5.0 4 Wash 0.5 15 sec 5 Wash 0.5 15 sec - After 4.6 m² had been processed, a number of visible dye particles had formed in the solutions of Tanks 2 and 3.
- The semi continuous batch was repeated except that tanks 1 and 2 also contained 0.5 g/l of compound 5 from Table I. After 18.6 m² of film had been processed, no dye particles were observed in any of the tanks.
- The semicontinuous batch was again repeated except that tank 3 instead of tanks 1 and 2 contained 0.5 g/l of compound 5 from Table I. After 9.3 m² of film had been processed, no dye particles were observed in any of the tanks.
- The effect of dye solubilizing compounds according to formula (I) from Table I on varying dyes in varying processing solutions was evaluated according to the following procedure.
- To 0.1 l of room temperature developer (D) or fixer (F) solutions of the formulations in Example 1, containing or not containing (as indicated in Table IV) 50 mg of Table I dye solubilizing compound, 5 mg of dyes D-1, D-2, or D-3 were added. Comparison compounds as shown in Table III were also tried as dye solubilizing compounds. The formation of dye particles was then determined by visual observation. The results are set forth in Table IV.
- The results presented in Table IV indicate that compounds according to formula (I) are significantly better dye solubilizing compounds than the comparison compounds.
Claims (11)
R₅ and R₆ are each independently hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, with the proviso that the dye solubilizing compound comprises at least four solubilizing groups as substituents on R₅'s or R₆'s that are alkyl or aryl wherein at least one of the solubilizing groups is anionic sulfo, and
that the cyanine dye is present in the processing solution at a concentration sufficient to cause formation of solid dye particles in the absence of the dye solubilizing compound.
R₇ and R₈ are each independently substituted or unsubstituted alkyl,
L₁, L₂, and L₃ are each independently substituted or unsubstituted methine linkages,
X is O, S, Se, -C-, or N-, and
n is 0, 1, or 2.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US20263288A | 1988-06-06 | 1988-06-06 | |
US202632 | 1988-06-06 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0346071A2 true EP0346071A2 (en) | 1989-12-13 |
EP0346071A3 EP0346071A3 (en) | 1991-02-27 |
EP0346071B1 EP0346071B1 (en) | 1996-03-13 |
Family
ID=22750685
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890305696 Expired - Lifetime EP0346071B1 (en) | 1988-06-06 | 1989-06-06 | Photographic process |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0346071B1 (en) |
JP (1) | JPH0228649A (en) |
CA (1) | CA1333967C (en) |
DE (1) | DE68925924T2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0652472A1 (en) * | 1993-09-16 | 1995-05-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
EP0971264A1 (en) * | 1998-07-06 | 2000-01-12 | Eastman Kodak Company | Concentrated photographic fixer additive and fixing compositions containing triazinylstilbene and method of photographic processing |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2576900B2 (en) * | 1988-05-09 | 1997-01-29 | 富士写真フイルム株式会社 | Development processing method of silver halide photosensitive material |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62166335A (en) * | 1986-01-20 | 1987-07-22 | Konishiroku Photo Ind Co Ltd | Color developer for silver halide color photographic sensitive material |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62257154A (en) * | 1986-04-30 | 1987-11-09 | Konika Corp | Processing method for silver halide color photographic sensitive material |
-
1989
- 1989-05-11 CA CA 599470 patent/CA1333967C/en not_active Expired - Fee Related
- 1989-06-05 JP JP14127289A patent/JPH0228649A/en active Pending
- 1989-06-06 DE DE1989625924 patent/DE68925924T2/en not_active Expired - Fee Related
- 1989-06-06 EP EP19890305696 patent/EP0346071B1/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62166335A (en) * | 1986-01-20 | 1987-07-22 | Konishiroku Photo Ind Co Ltd | Color developer for silver halide color photographic sensitive material |
Non-Patent Citations (1)
Title |
---|
RESEARCH DISCLOSURE. no. 207, July 1981, HAVANT GB page 268 C.R.Cappel, M.D.Purol: "Methods of reducing spectral sensitizing dye stain in photographic elements" * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0652472A1 (en) * | 1993-09-16 | 1995-05-10 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
EP0971264A1 (en) * | 1998-07-06 | 2000-01-12 | Eastman Kodak Company | Concentrated photographic fixer additive and fixing compositions containing triazinylstilbene and method of photographic processing |
Also Published As
Publication number | Publication date |
---|---|
EP0346071B1 (en) | 1996-03-13 |
EP0346071A3 (en) | 1991-02-27 |
CA1333967C (en) | 1995-01-17 |
DE68925924T2 (en) | 1996-09-05 |
JPH0228649A (en) | 1990-01-30 |
DE68925924D1 (en) | 1996-04-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4521508A (en) | Silver halide photographic light-sensitive materials | |
US3575704A (en) | High contrast light sensitive materials | |
EP0317950B1 (en) | Photographic elements containing a bleach accelerator precursor | |
EP0498302A1 (en) | Silver halide emulsions for use in processing involving solution physical development | |
DE68922239T2 (en) | Silver halide photographic materials. | |
EP0351593A2 (en) | Light-handleable photographic element having solid particle dispersion filter dye layer | |
US3816121A (en) | Direct positive photographic material containing a color coupler under one micron in size and fogged silver halide grains with substantially no internal sensitivity having absorbed on the surface a desensitizing dye containing a solubilizing group | |
EP0346071B1 (en) | Photographic process | |
EP0605917B1 (en) | Red sensitizers for high silver chloride emulsions | |
EP0304323B1 (en) | Direct positive silver halide light-sensitive colour photographic material | |
US5238793A (en) | Photographic process | |
JPH01280750A (en) | Silver halide photographic sensitive material | |
EP0017148B1 (en) | Internally doped high chloride silver halide emulsions, processes for their preparation and photographic elements | |
US4506008A (en) | Silver halide photographic light-sensitive materials | |
JPH07199390A (en) | Photograph element and photograph method | |
JP2831020B2 (en) | Sensitizing fee for high chloride silver halide photographic compositions | |
US3854949A (en) | Silver halide photographic compositions and processes for obtaining positive images | |
JPS5856857B2 (en) | Processing method for silver halide photographic materials | |
CA1146001A (en) | High contrast photographic emulsions containing a phenyl hydrazine derivative | |
US5077190A (en) | Process for spectral sensitization of a silver halide emulsion | |
DE69605222T2 (en) | Color reversal elements containing a compound releasing a bleach accelerator | |
US4808516A (en) | Photographic emulsion and element | |
EP0328391A2 (en) | Stabilizers for photographic emulsions | |
US4539291A (en) | Direct positive silver halide photographic materials | |
US5389507A (en) | Reversal elements with internal latent image forming core-shell emulsions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19910819 |
|
17Q | First examination report despatched |
Effective date: 19940516 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): BE CH DE FR GB LI NL |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE FR GB LI NL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19960313 Ref country code: CH Effective date: 19960313 |
|
REF | Corresponds to: |
Ref document number: 68925924 Country of ref document: DE Date of ref document: 19960418 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19970331 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19970610 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19980505 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19980625 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990226 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19990101 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990606 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19990606 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000503 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20000714 Year of fee payment: 12 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010630 |
|
BERE | Be: lapsed |
Owner name: EASTMAN KODAK CY (A NEW JERSEY CORP.) Effective date: 20010630 |