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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
  • G03C5/383—Developing-fixing, i.e. mono-baths
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers
  • G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents
• • 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
  • G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development

Definitions

• ABSTRACT OF THE DISCLOSURE Stabilized photographic physical developers containing a superadditive combination of ionic surfactant and organic antifoggant.
• This invention concerns physical developers for photographic images, and more particularly, physical developers stabilized with surface active agents. 7
• photographic images can also be produced by means of a physical developer.
• chemi cal developers act on silver salts of the image-forming layer to form density in image areas
• physical developers in principle contain dissolved silver salts as well as the silver halide developing agents. These have been described in H-ornsby Basic Photographic Chemistry, 1956, Fountain Press, London, England.
• One object of this invention is to provide 'a stable physical developer solution of good developing activity having a useful life of from several hours to several days. Another object is to provide stable monobaths which in the unused state may be stored several months without sludge formation. An additional object is to improve the development selectivity of physical developers so that they will deposit metal only 'where there are active nuclei and not in other areas of the image forming layers.
• physical developers may be defined as those developing solutions wherein substantially all of the metal for development is contained as a soluble reducible salt in the solution.
• a particular solution should contain at least 5X10 moles per liter of reducible metal (silver) salt before its initial use. This distinguishes physical developers from the developing solutions which are monobaths, since monobaths initially contain no reducible metal (silver) ion before use. After a monobath has been used many times for the development of silver halide layers, a considerable silver concentration may be built up in the monobath because of the solvent activity of the solution. My invention is also applicable to such solutions.
• the physical developers which are useful in the invention must contain a reducible metal ion (silver) and one or more silver halide developing agents known in the art.
• the reducible metal ions may be any of those which can be reduced to the metal by any of the wellknown photographic developing agents.
• the reducible metal salt is a water soluble silver salt usually silver nitrate.
• other soluble silver salts may be used as Well as salts of metals such as copper, mercury, platinum, gold, palladium, etc.
• the photographic developing agent may be a dihydroxy-benzene type or the like.
• Typical useful developers include hydroquinone, catechol, ascorbic acid, isoascorbic acid, pyrocatechol, gallic acid, gentistic acid, pyrogallol, etc.
• Paraphenylenediamine type silver halide developers may be used selected from those which are known inthe art.
• aminophenol types may be used such as p-methylaminophenol sulfate, o-a-mino' phenol, p-hydroxyphenylglycine, etc.
• auxiliary developers may be used also, such as the pyrazolidone type materials, and a combination may be used of more than one type of the various types referred to above as well as a combination of developers with auxiliary developing agents.
• Various compounds may be included in the physical developer solution such as compounds intended to control the pH, particularly those used for buffering the solution, sulfite to improve the stability, a halogen salt, etc.
• Typical agents are silver complexing agents such as sodium thiosulfate and the like.
• the particular silver complexing agent may be selected from one or more of those known in the art as silver halide complexing agents.
• Physical developers may be used wherever nuclei are present as sites for physical development. For instance,
• these developers may be used to intensify chemically developed silver images, to develop light activated nuclei such as zinc oxide, zinc hydroxide, titanium dioxide, etc. They may also be used with systems wherein nuclei are treated with light-sensitive substances rendering the nuclei inactive as sites until exposed to light, as described in Gilman et al., US. Ser. No. 332,305, filed December 20, 1963, now US. Patent No. 3,330,- 658. In a related system the nuclei are rendered inactive by exposure to light as described in Hanson et al., US. Ser. No. 266,328, filed March 19, 1963, now US. Patent No. 3,320,064, and the active nucleiare developed using a physical developer.
• Surfactants which are useful in stabilizing physical developers include ionic surfactants or surface-active substances which are adsorbed at the boundary surface of two phases. These are usually organic compounds which contain both one or more hydrophilic and one or more hydrophobic groups, which are bonded together either directly or, for example, by an ester, ether or amide bond.
• the hydrophobic groups may be, for example, aliphatic carbon chains having from 8 to 18 carbon atoms in contradistinction to the hydrophilic groups. The latter are therefore sometimes referred to as solubilizing or polar groups. These may be, for example, sulphonate 'or pyridinium groups.
• the surfactants may further be defined as ionic surfactants, the hydrophilic group of which carries the Charge and which thus occur in the form of an anion, a cation or a Zwitterion. These are referred to as anion-active, cation-active and amphoteric surfactants, respectively. Non-ionic species, however, are ineffective.
• surfactants are typical of those which may be used to stabilize physical developers.
• the life of the surfactant stabilized developer may be further increased by the addition of photographic chemicals generally recognized as antifogging agents.
• photographic chemicals generally recognized as antifogging agents.
• the effect of such addition of both surfactant and antifogging agent produces stabilization beyond that expected from simple additivity.
• Sufiicient antifoggant is used to increase the life of the surfactant-stabilized developer at least 50% when compared to the identical developer as described above which has been surfactant stabilized.
• Organic reagents which are useful in our invention a e selected from those antifoggants which are customarily used for lowering fog in the photographic art.
• my invention concerns antifoggants which are water dispersible organic compounds which form complexes with ionic silver, said complexes form a non-reducible layer which tends to insulate the metal nuclei and to prevent them from acting as catalytic centers for physical development.
• inorganic salts particularly bromides and iodides exhibit marked antifogging properties.
• My invention is not directed toward such inorganic salts, but is limited to organic compounds of the type to be described below.
• antifoggants As a further description of antifoggants, it has been indicated that they are compounds which form silver salts of solubility in the same range as or less than silver chloride. Antifoggants cover a varied group of compounds, many of which are listed in Mees, The Theory of the Photographic Process, page 679, 1954, and in Glafkides, Photographic Chemistry, volume I, 1958, beginning at page 374.
• antifoggants are intended to be illustrative of those which may be used depending upon the surfactant and the physical developer:
• Cyclic amines for example, diphenylamine and benzidine derivatives having at least two NH groups
• Iminazoles for example, 6 nitrobenziminazole, p-nitrobenziminazole, etc.
• Mercaptobenziminazole for example, 2-thio 4 methyl 5 acetyliminazole, 3-allyl- Z-dimethyl-Z-thiohydantoine, etc.
• Triazoles for example, benzotriazole, 5 methylbenzotriazole, p-nitro-4-azimidobenzene, etc.
• Tetrazoles for example, l-phenyl 5 mercaptotetrazole, 5 phenyltetrazole, 5 (m-nitrophenyl)- tetrazole, etc.
• (E) Thiazoles for example, 2 methylbenzthiazole, including the mcthiodide (or ethyl-p-toluenesulphonate) or 2 methyl-benzthiazole, 2 amino 4 methylthiazole, 2 diethylamino 4 methylthiazole, 2 aminothiazole- 5:4':5:6-quinoline, 2 thio 4 methyl and 2-thione-3- benzyl 4 methylthiazole, 2 benzylidenehydrazino-4- oxathiazoles, etc.
• 2 methylbenzthiazole including the mcthiodide (or ethyl-p-toluenesulphonate) or 2 methyl-benzthiazole, 2 amino 4 methylthiazole, 2 diethylamino 4 methylthiazole, 2 aminothiazole- 5:4':5:6-quinoline, 2 thio 4 methyl and 2-thione-3- benzyl 4 methylthi
• F Mercaptobenzthiazoles for example mercaptobenzthiazole, 2 methylmercaptobenzthiazole, N-ethyl mercaptobenzthiazole, N-benzyl mercaptobenzthiazole, etc.
• (K) Iodonium derivatives for example, diphenyliodonium nitrate, 4-(2':4'-diiodophenoxy) quinaldinic acid, etc.
• (L) Thiobarbituric acids for example, thiobarbituric acids, phenyl-thiobarbituric acid, Z-hydroxylidine-thiobarbituric acid, 3 methoxy 4 hydroxybenzylidinethiobarbituric acid, etc.
• Alaloids for example, the hydrochlorides of quinine and quinidine, morpholine' derivatives such as phenylmorpholine, 2v aminothiazole 5:6:526 hydrocinchonidine and its derivatives, 2-picolic acid, etc.
• antifoggants which can be used are directed to those which are compatible with the physical developer and with the surfactant or surfactants which are also present as stabilizing agents.
• a portion (200 milliliters) of the complete physical developer is placed in a glass cell with an optical path of two inches.
• a SOO-watt lamp is placed on one side of the cell and a light meter on the other (length from lamp to meter is 12 inches).
• the solution is continuously agitated and the change in transmittance observed.
• the sample is considered sludged. The time required for this degree of sludge is used to calculate the stabilization factor.
• the stabilization factor is the time required for a stabilized developer to sludge divided by the time for the control developer to sludge.
• the superadditive stabilization factor is calculated by dividing the time for the control developer to sludge into the time for the developer to sludge when both surfactant and antifoggant are present. A superadditive effect is observed when the sum of the stabilization factors of the developer with surfactant alone and developer with antifoggant alone is less than the stabilization factor of the developer containing the surfactant and antifoggant in combination.
• Hyamine 10X do i 5-Iuethylbenzotriazole. 1. 3 .i- Hyamine 10X o None 2-methylbenzothiazole. 1i 6 Hyamine 10X do 8 None t Salieylaldehyde semlcarbazone 1. 6 Hyamine 10X do t t 11 one B-mercaptopurine. 12 Hyamine 10X one Hyamine 10X.
• the stabilization factors for each of the combinations shown above indicate the marked improvement in stability of the physical developing solutions when both surfactant and antifoggant are present.
• the images developed in the physical developer were of higher quality (had higher actuance) than those developed in the control.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant and at least one organic antifoggant, said antifoggant being present in an amount suflicient to increase the life of the developer at least 50% when compared to the life of an identical developer containing the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent selected from the group consisting of N-methylaminophenol sulfate, pyrogallol, N,N-dimethyl-pphenylenediamine, phenyl-1-pyrazolidone-3, hydroquinone, pyrocatechol, o-aminophenol, ascorbic acid, N-p-hydroxyphenylglycine and N-N-diethyl-p-phenylenediarnine, at least one ionic surfactant and at least one organic antifoggant, said antifoggant being present in an amount suflicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a photographic reducing agent selected from the group consisting of N-methylaminophenol sulfate, pyrogallol, N,N-dimethyl-pphenyl
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant and an iminazole antifoggant, said antifoggant being present in an amount sufiicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt .reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant and a triazole antifoggant, said antifoggant being present in an amount sufiicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant and a tetrazole antifoggant, said antifoggant being present in an amount sufficient to increase the life of the developer at least 50% when compared to the life of an identical developer containing said surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant and a thiazole antifoggant, said antifoggant being present in an amount sufiicient to increase the life of the developer at least 50% when compared to the life of an identical developer containing said surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant and an oxazole antifoggant, said antifoggant being present in an amount sufiicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant, and a semicarbazide antifoggant, said antifoggant being present in an amount sufficient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a Water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant, and a pyrimidine antifoggant, said antifoggant being present in an amount sufficient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant, and a thiazolidine antifoggant, said antifoggant being present in an amount sufficient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant, and an iodonium antifoggant, said antifog gant being present in an amount suflicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer com prising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, an ionic surfactant and a thiobarbituric acid antifoggant, said antifoggant being present in an amount sufiicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant, and a benzene-sulphinic acid antifoggant, said antifoggant being present in an amount sufiicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant and an alkaloid antifoggant, said antifoggant being present in an amount sufficient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of water soluble metal salt reducible to metal, a photographic reducing agent, for reducing said metal salt to metal, at least one ionic surfactant, and a thioanilide antifoggant, said antifoggant being present in an amount sutficient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant, and a pyrazoline antifoggant, said antifoggant being present in an amount sufiicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant, and an acetylene dicarboxylic acid antifoggant, said antifoggant present in an amount sufficient to increase the life of the developer at least 50% when com- 12 pared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant and a degraded protein antifoggant selected from the group consisting of cysteine hydrochloride and histidine hydrochloride, said antifoggant being present in an amount sufficient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic physical developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to to metal, at least one ionic surfactant, and an antifoggant, selected from the group consisting of benzotriazole and S-methylbenzotriazole, said antifoggant being present in an amount suflicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.
• a stabilized photographic developer comprising an aqueous solution of a water soluble metal salt reducible to metal, a photographic reducing agent for reducing said metal salt to metal, at least one ionic surfactant, and at least one cyclic amine antifoggant, said antifoggant being present in an amount sufiicient to increase the life of the developer at least 50% when compared to the life of an identical developer stabilized with the surfactant.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Developing Agents For Electrophotography (AREA)

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Applications Claiming Priority (1)

Publications (1)

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Cited By (8)

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Citations (4)

• 1965
  • 1965-10-04 US US492834A patent/US3390998A/en not_active Expired - Lifetime
• 1966
  • 1966-10-03 DE DE19661547735 patent/DE1547735A1/de active Pending
  • 1966-10-03 BE BE687743D patent/BE687743A/xx unknown
  • 1966-10-03 FR FR78511A patent/FR1495752A/fr not_active Expired
  • 1966-10-04 GB GB44269/66A patent/GB1166045A/en not_active Expired

Patent Citations (4)

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