Classifications

• • 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
  • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile 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
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D263/46—Sulfur atoms
• • 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
  • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
  • C07D277/70—Sulfur atoms
  • C07D277/74—Sulfur atoms substituted by carbon atoms
• • 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
  • 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

Definitions

• the present invention relates to the use of anti-fogging and stabilizing agents for photographic silver halide emul' sions and, more particularly, to the use of sulfoalkyl-Z- thiazolyland oxazolylthio ethers, their salts and esters for such purpose.
• Benzthiazole and its derivatives such as Z-mercaptobenzthiazole, have been recommended as being etfective in preventing any increase in fog through stabilizing or controlling the keeping qualities of light-sensitive silver halide emulsions. Although these compounds have the ability to reduce fog tendencies and to improve stability, they are deficient in that they lower the sensitivity of the emulsions and in many cases reduce optical and dye sensitivity.
• sulfoalkyl-Z-thiazolylthio ethers and the corresponding oxazolylthio ethers, their salts and esters are not only excellent stabilizers or antifogging agents for light-sensitive silver halide emulsions but, in addition, they have the faculty of performing this function without lowering the sensitivity of the emulsion with which they are associated or without reducing the sensitivity of the emulsion to light of longer wave length attributable to the presence of sensitizing dyes.
• antifoggants the use of which is contemplated herein, may be represented by the following formula:
• R is hydrogen, an aliphatic radical such as 'alkyl, i.e., methyl, ethyl, propyl, butyl, amyl and the like; hydroxyalkyl, i.e., hydroxymethyl, hydroxyethyl and the like; carboxyalkyl, i.e., carboxymethyl, carboxyethyl and the like; aryl such as phenyl, toluyl, naphthyl, carboxyphenyl, sulfophenyl and the like; aralkyl such as benzyl or a salt-forming group such as sodium, potassium, ammonium, silver or the like; R is hydrogen, alkyl as above, aryl as above or carboxyalkyl as above or both Rs together form a fused-on aromatic ring such as benzo or naphtho, said benzo or naphtho ring if desired bearing a substituent such as halogen, i.e., chloro,
• the product After allowing the mixture to stand overnight, the product is filtered and dried. It may be recrystallized from ethanol and dried at room temperature.
• the product was obtained in this procedure in the form of its alkali metal salt. If the free acid be desired, it is obtained by passing a solution of the alkali metal salt through an anion exchange resin such as those described in US. Patent 2,732,352 or 2,591,573.
• esters may be produced in the conventional manner by refluxing the free acid with the desired alcohol or phenol in the presence of hydrochloric acid.
• the concentration used depends very much on the type of emulsion employed and it is advisable to determine the optimum concentration from case to case.
• the antifoggant in layers adjacent to the emulsion, that is, in a separate undercoating layer or in the anti-abrasion gelatin surface.
• the desired result may be obtained by adding the antifoggant to one or several of the processing baths, i.e., developer or fixer for the involved emulsion.
• antifoggants and stabilizers may be employed in connection with any type of photographic emulsion, e.g., non-sensitized, orthochromatic, panchromatic, X-ray emulsions, paper emulsions, color emulsions or the like. They may be used in combination with other known antifoggants and stabilizers, reductionand metaland noble metal sensitizers or in combination with hydroxypolyethenoxy derivatives, i.e., those obtained by reacting ethyleneoxide with an alcohol, phenol, amine or the like (see US. Patent 1,970,578).
• Example I A silver halide emulsion in gelatin containing 2% silver iodide and 98% silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. It was then readied for coating, finals were added such as sensitizing dyes, and hardening agents. A 1% solution of the sodium salt of fi-(Z-benzthiazolyhmercaptoethanesulfonic acid in water was prepared and added to the emulsion as an antifoggant and stabilizer. The emulsion samples contained about .4 mol of silver halide. The so prepared emulsion samples were coated on a suitable cellulose ester base and dried. Samples of these coatings were then exposed in a type IIB sensitometer and developed in a developer of the following composition:
• Example 11 4 that the sodium salt of p-(2-benzthiazolyl)-mercaptoethanesulfonic acid was replaced by an equivalent quantity of fl(2-benzoxazolyl)mercaptoethanesulfonic acid sodium salt.
• the benzoxazolyl derivates was prepared in the same fashion as the benzthiazolyl derivate excepting that the Z-mercaptobenzthiazole was replaced by an equivalent quantity of Z-mercaptobenzoxazole.
• Example III The procedure was the same as in Example I excepting that there was employed as the antifoggant -(2-benzthiazolyl)-mercaptopropanesulfonic acid. The results were similar to those of Example I.
• the antifoggant of this example was prepared in the same manner as that of Example I excepting that the 2-bromoethanesulfonic acid sodium salt was replaced by an equivalent quantity of 'y-bromopropanesulfonic acid sodium salt.
• Example IV Exposed samples of a photographic film were developed for twelve minutes at 65 F. in a standard metolhydroquinone developer. Two tests were made, one with the normal developing solution and one with a developer containing mgs. of the sodium salt of fl-(2-benzthiazolyl)mercaptoethanesulfonic acid per one liter of developer. Sensitometric strips, developed in the normal developer (control) for twelve minutes showed a fog of .30, whereas those strips which were developed in the developer containing the antifoggant had a fog of .20.
• Example V The procedure was the same as in Example IV excepting that the )3-(2-benzthiazolyl)mercaptoethanesulfonic acid was replaced by an equivalent quantity of p-(2-benzoxazolyl)mercaptoethanesulfonic acid. The results were substantially the same as those obtained in Example IV.
• a light-sensitive photographic material comprising a base and a light-sensitive silver halide emulsion thereon, said light-sensitive material containing as an antifoggant a compound selected from the class consisting of those of the following formulae:
• R is selected from the class consisting of hydrogen, alkyl, hydroxylalkyl, carboxyalkyl, aryl, aralkyl and a cation; R is selected from the class consisting of hydrogen, alkyl, aryl and carboxyalkyl; X represents the atoms necessary to complete a nucleus selected from the class consisting of those of the benzene and naphthalene series; Y is selected from the class consisting of oxygen and sulfur and n is a whole number of from 2 to 3 2.
• said antifoggant is located in the silver halide emulsion.
• a light-sensitive photographic material comprising a base with a light-sensitive silver halide emulsion thereon, said emulsion containing as an antifoggant the compound B-(Z-benzthiazolyl)mercaptoethanesulfonic acid sodium salt of the formula:
• R is selected from the class consisting of hydrogen, an alkyl, hydroxyalkyl, carboxyalkyl, aryl, aralkyl and a cation; R is selected from the class consisting of 1 References Cited in the file of this patent UNITED STATES PATENTS 2,186,849 Wilmanns et al. Jan. 9, 1940 2,490,745 Carroll et al. Dec. 6, 1949 2,697,100 Knott Dec, 14, 1954 2,819,965 Murray et al. Jan. 14, 1958 2,915,395 Popeck et al Dec. 1, 1958 FOREIGN PATENTS 973,727 France Sept. 20, 1950

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• 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)
• Thiazole And Isothizaole Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (10)

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• 0
  • BE BE572846D patent/BE572846A/xx unknown
• 1957
  • 1957-12-26 US US705145A patent/US2902367A/en not_active Expired - Lifetime
  • 1957-12-26 US US705151A patent/US3042521A/en not_active Expired - Lifetime
• 1958
  • 1958-12-23 DE DEG26026A patent/DE1093205B/de active Pending

Patent Citations (6)

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