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
  • G03C5/39—Stabilising, i.e. fixing without washing out
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
  • C07C335/30—Isothioureas
  • C07C335/32—Isothioureas having sulfur atoms of isothiourea groups bound to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F28/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
• • 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
  • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/835—Macromolecular substances therefor, e.g. mordants

Definitions

• This invention relates to photographic elements, and more particularly to the stabilization of photographic elements.
• Another object of our invention is to provide photographic silver halide emulsions containing certain polymers which function to stabilize developed silver images.
• a further object of our invention is to stabilize photographic silver images wit-h certain polymers. Other objects of our invention will appear herein.
• R represents H or a lower alkyl group, such as methyl, ethyl, propyl or hutyl, preferably methyl or ethyl;
• R represents an alkylene group preferably of 2 to carbon atoms, but which may contain up to 12 or more carbon atoms, such as ethylene, propylene, butylene, hexylene, octylene and dodecylene;
• A is an anion, such as halide, p-toluene sulfonate or methanesul-fonate; and
• n is a whole number, such as 5 to 100,000 or more.
• the silver image of a photographic element is stabilized against oxidative degradation by bathing the photographic element in a solvent solution of the isothiuronium salt containing polymers described above.
• Example 1 shows the antifoggant activity in photographic emulsions of the polymers used in the invention.
• the resulting emulsions were coated on a support at the rate of 432 mg. silver and 980 mg. gelatin per square foot, exposed and developed for 5 minutes in Kodak Developer DK-50. The samples were incubated for one week at 100 F. and 50% relative humidity. The results are shown in Table I.
• Examples 2-5 illustrate the superior stability of silver images produced from silver halide emulsions containing polymers having isothiuronium salt groups.
• EXAMPLE 3 Ten grams of poly(2[2-(methacryloyloxy)ethyl]isothiuronium met-hanesulfonate were added to a sensitized emulsion, exposed and processed. The image had a colder tone than that of the control, and showed outstanding resistance to hydrogen peroxide vapor attack when tested as described in Example 2.
• EXAMPLE 5 Ten grams of poly(2-[3-(methacryloyloxy)propyl] isothiuronium p-toluene sulfonate) were substituted for the polymer employed in Example 3. The image had a colder tone than the control, and had good resistance to hydrogen peroxide vapor attack when tested as described in Example 2.
• EXAMPLE 6 A one percent solution of copoly(N,N-dimethylacrylamide-ethyl acrylate 2[2 (methacryloyloxy)ethyl]isothiuronium methane sulfonate) (50:30:20 by weight) in water was used to bathe "two strips of an exposed, developed and fixed panchromatic sulfur and gold sensitized silver chlorobromide microfilm containing silver images. The strips were bathed in the solution for 5 minutes at 68 'F. One strip of the treated film was then rinsed for one second in water, the other was rinsed for 5 minutes in running water, and both were dried at 68 F. Both strips were then subjected to a 24-hour hydrogen peroxide vapor test in the presence of acetic acid vapor. The strips were both essentially free from peroxide attack, whereas an untreated control was severely attacked.
• the polymers useful in this invention may consist solely of repeating units which are isothiuronium salts. Copolymers are also useful in which at least one-third of the repeating units are isothiuronium salts; the remaining repeating units may be any suitable divalent moiety, such as those represented by the formula:
• A, B, D, and E are substituents which do not exert any detrimental effect on photographic emulsions, or are substituents which are not detrimental to silver images when the polymers are employed in post-processing baths.
• copolymers employed in the examples are described by weight ratios of reactants. In all of these copolymers, at least one-third of the repeating units are isothiuronium salts.
• the polymers employed in this invention may be prepared in any convenient manner, such as by the method described by Dykstra and Smith in their patent application filed on the same date as the present application.
• a convenient method is to prepare a monomer having the formula:
• R is H or alkyl, R is alkylene and A is an anion, by forming a sulfonate ester of a compound having the formula:
• the monomer may then be polymerized alone or with a copolymerizable monomer.
• the polymers employed in this invention are not removed from photographic emulsions during processing, but remain in the finished product functioning to promote image stability, for example, against oxidative degradation.
• the most useful concentration range of the polymers in photographic silver halide emulsions, to provide antifoggant activity and image stability, is from about 1 to 20 grams polymer per mole of siver; preferably, we employ about 5 to grams of polymer per mole of silver.
• silver images may be stabilized by bathing in a solution containing the polymers described above.
• the duration of effective treatment varies according to the particular polymer employed and the concentration thereof in the solution. Any solvent may be employed which is not detrimental to the photographic element.
• This invention is broadly applicable to photographic silver halide emulsions and to stabilizing the silver image obtained from them. It has special utility for sensitized, particularly sulfur-gold sensitized, silver chlorobromide emulsions, e.g., microfilms having such emulsions.
• a photographic silver halide emulsion having incorporated therein a stabilizing quantity of a polymer in which at least one-third of the repeating units have the following formula;
• R is selected from the group consisting of hydrogen and alkyl, R is alkylene, n is a whole number, and A is an anion.
• a photographic silver halide emulsion having incorporated therein a stabilizing quantity of copoly(N,N- dimethylacrylamide-ethyl acrylate 2 [Z-(methacryloyloxy) ethyl]isothiuronium salt, at least one-third of the repeating units of the polymer being isothiuronium salt units.
• a photographic silver halide emulsion having incorporated therein a stabilizing quantity of poly(2[2-methacryloyloxy) ethyl] isothiuronium salt.
• a photographic silver chlorobromide emulsion having incorporated therein a stabilizing quantity of copoly (N,N-dimethylacrylamide-ethyl acrylate-Z [2 (methacryloyloxy)ethyl]isothiuronium p-toluene sulfonate, at least one-third of the repeating units of the polymer being isothiuronium salt units.
• a photographic silver halide emulsion having incorporated therein a stabilizing quantity of poly(2-[3- (methacryloyloxy propyl] isothiuronium salt.
• R is selected from the group consisting of hydrogen and alkyl, R is alkylene, n is a whole number, and A is an anion.
• the method of stabilizing the silver image of a photographic element which comprises bathing the photographic element in a solvent solution of copoly(N,N- dimethylacrylamide-et'hyl acrylate 2 [Z-(methacryloyloxy)ethyl]isothiuronium salt), at least one-third of the repeating units of the polymer being isothiuronium salt units.
• the method of stabilizing the silver image of a photographic element which comprises bathing the photographic element in a solvent solution of poly(2-[2-(methacryloyloxy) ethyl] isothiuronium salt) 9.
• the method of stabilizing the silver image of a photographic element which comprises bathing the photographic element in a solvent solution of copoly(N,N-dimethylacrylamide-ethyl acrylate 2 [Z-(methacryloyloxy)ethyl]isothiuronium p-toluene sulfonate), at least one-third of the repeating units of the polymer being isothiuronium salt units.

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• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Organic Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)

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• 1965
  • 1965-02-10 US US431701A patent/US3375115A/en not_active Expired - Lifetime
  • 1965-02-10 US US431702A patent/US3306884A/en not_active Expired - Lifetime
• 1966
  • 1966-02-04 BE BE676102D patent/BE676102A/xx unknown
  • 1966-02-07 DE DE19661595562 patent/DE1595562B1/de active Pending
  • 1966-02-07 DE DE19661547665 patent/DE1547665A1/de active Pending
  • 1966-02-10 GB GB5814/66A patent/GB1131275A/en not_active Expired

Non-Patent Citations (1)

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