US2743184A - Photographic antiplumming agents and emulsions containing them - Google Patents

Photographic antiplumming agents and emulsions containing them Download PDF

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Publication number
US2743184A
US2743184A US427373A US42737354A US2743184A US 2743184 A US2743184 A US 2743184A US 427373 A US427373 A US 427373A US 42737354 A US42737354 A US 42737354A US 2743184 A US2743184 A US 2743184A
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Prior art keywords
photographic
agents
silver halide
antiplumming
emulsion
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US427373A
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William B Kendall
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE537818D priority Critical patent/BE537818A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US427373A priority patent/US2743184A/en
Priority to GB12401/55A priority patent/GB774618A/en
Priority to DEE10662A priority patent/DE1005839B/en
Priority to FR1123458D priority patent/FR1123458A/en
Application granted granted Critical
Publication of US2743184A publication Critical patent/US2743184A/en
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Expired - Lifetime legal-status Critical Current

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    • 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
    • G03C1/35—Antiplumming agents, i.e. antibronzing agents; Toners
    • G03C1/355—Organic derivatives of bivalent sulfur, selenium or tellurium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/13—Antibronze agent or process

Definitions

  • This invention relates to improvements in the production of photographic images, such as images on paper supports, prepared from silver halide emulsions. More particularly this invention relates to silver halide emulsions having associated therewith a novel antiplumming or antibronzing compound which prevents image degradation of an exposed silver halide emulsion during processmg.
  • Silver halide emulsions after exposure often are subject to image degradation during processing, that is, during development, fixing, washing, toning, etc., and particularly When they encounter the moist heat to which they are subjected on drying as when prints are subjected to ferrotyping or hot glazing. This degradation of the image frequently manifests itself as plumming or bronzing.
  • An object of the present invention is to provide a novel method of producing photographic images of superior quality. Another object is to provide a method for preventing image degradation of an exposed silver halide emulsion during processing. Still another object is to prevent plumming or bronzing of photographic prints during a hot glazing process. Another object of the invention is to provide compounds suitable for use as antiplumming agents in silver halide emulsions. Other objects will appear hereinafter.
  • endothiophenyl thiadiazoline thiol and its potassium salt, are effective antiplumming agents when employed with silver halide photographic emulsions during processing of an exposed silver halide emulsion which term includes one or more of the operations of developing, fixing, washing and drying.
  • Potassium endothiophenyl thiadiazoline thiol may be prepared by the method described in J. Prakt. Chem, 60, 206 (1899).
  • Potassium ethyl xanthate was prepared by adding 30 g. of carbon bisulfide to a solution of 16 g. of potassium hydroxide in 50 m1. of ethanol. To the resulting slurry, a solution of 20 g. of freshly-distilled phenylhydrazine in 60 ml. of ethanol was added gradually. The mixture at first thinned out, and then set up again. It was heated with stirring, on the steam bath for four hours, then half of the solvent was distilled off, and the solution cooled in an ice bath. The white, crystalline potassium salt which separated was removed by filtration, washed with a little cold alcohol, and finally with ether.
  • the free endothiphenylthiadiazolinethiol may be prepared by treating the potassium salt thereof with hydrochloric acid.
  • these compounds may be added preferably to the emulsion layer or layers. They are also elfective if added to the developing solution, or to other layers carried on the I sensitive emulsion support such as the backing layer or supercoat. Alternately the sensitive layer may be bathed in a solution of theagent after exposure but prior to development. amounts between 0.1 and 4.0 grams per, molof silver halide in the emulsion.
  • Example 1 An emulsion was prepared in accordance with Examples l of U. S. Patent 2,596,756. To separate portions .of this emulsion were added quantities of a 1:500 aqueous solution of potassium endothiophenyl thiadiazoline thiol equivalent to 0, 0.5, 1.0 .and 2.0 grams per mol of silver.
  • An emulsion was prepared according to Example 1 of U. S. Patent 2,596,756. To portions of this emulsion were added quantities of a 1:200 solution of endothiophenylthiadiazoline thiol dissolved in equal parts of methanol and acetone, and equivalent to 0, 0.5 and 2.0 g./mol of silver. These emulsions were then coated on glossy baryta-coated single-weight paper at a rate of 650 ft. mol of silver. Two samples of each coating were exposed through a step wedge, developed, fixed and washed. One set of prints was dried without heat, and the other Patented Apr.
  • the method'of preventing'image degradation of an exposed silver halide emulsion during drying which comprises performing at least one of the steps of developing,
  • a photographic silver halide emulsion containing from 0.1 and 4.0 grams per mol of silver halide of a compound having the formula:

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)

Description

United States Patent PHOTOGRAPHIC ANTIPLUMMINGAGENTS AND EMULSIONS CONTAINING THEM William B. Kendall, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application May 3, 1954, Serial No. 427,373
3 Claims. (Cl. 957) This invention relates to improvements in the production of photographic images, such as images on paper supports, prepared from silver halide emulsions. More particularly this invention relates to silver halide emulsions having associated therewith a novel antiplumming or antibronzing compound which prevents image degradation of an exposed silver halide emulsion during processmg.
Silver halide emulsions after exposure often are subject to image degradation during processing, that is, during development, fixing, washing, toning, etc., and particularly When they encounter the moist heat to which they are subjected on drying as when prints are subjected to ferrotyping or hot glazing. This degradation of the image frequently manifests itself as plumming or bronzing.
Heretofore, various compounds have been proposed for use with silver halide emulsions to overcome such plumming and bronzing effects.
An object of the present invention is to provide a novel method of producing photographic images of superior quality. Another object is to provide a method for preventing image degradation of an exposed silver halide emulsion during processing. Still another object is to prevent plumming or bronzing of photographic prints during a hot glazing process. Another object of the invention is to provide compounds suitable for use as antiplumming agents in silver halide emulsions. Other objects will appear hereinafter.
In accordance with the present invention I have found that endothiophenyl thiadiazoline thiol, and its potassium salt, are effective antiplumming agents when employed with silver halide photographic emulsions during processing of an exposed silver halide emulsion which term includes one or more of the operations of developing, fixing, washing and drying.
Potassium endothiophenyl thiadiazoline thiol may be prepared by the method described in J. Prakt. Chem, 60, 206 (1899).
C H NHNH 20S KOH o 5 s 2 K S SE Potassium ethyl xanthate was prepared by adding 30 g. of carbon bisulfide to a solution of 16 g. of potassium hydroxide in 50 m1. of ethanol. To the resulting slurry, a solution of 20 g. of freshly-distilled phenylhydrazine in 60 ml. of ethanol was added gradually. The mixture at first thinned out, and then set up again. It was heated with stirring, on the steam bath for four hours, then half of the solvent was distilled off, and the solution cooled in an ice bath. The white, crystalline potassium salt which separated was removed by filtration, washed with a little cold alcohol, and finally with ether.
The free endothiphenylthiadiazolinethiol may be prepared by treating the potassium salt thereof with hydrochloric acid.
In employing these compounds as anti-plumming or anti-bronzing agents either one of them, or a suitable mixture thereof, may be added preferably to the emulsion layer or layers. They are also elfective if added to the developing solution, or to other layers carried on the I sensitive emulsion support such as the backing layer or supercoat. Alternately the sensitive layer may be bathed in a solution of theagent after exposure but prior to development. amounts between 0.1 and 4.0 grams per, molof silver halide in the emulsion. I
These two compounds are very effective an anti-plumming agents when employed in any of the ways herein described including bathing the developed image in a solution of the compound after fixation. Asuitable bath for example in an aqueous solution containing 0.5 to 2.0 .1
grams per liter of the compounds.
amples Example 1 An emulsion was prepared in accordance with Examples l of U. S. Patent 2,596,756. To separate portions .of this emulsion were added quantities of a 1:500 aqueous solution of potassium endothiophenyl thiadiazoline thiol equivalent to 0, 0.5, 1.0 .and 2.0 grams per mol of silver.
These separate portions were then coated on separate sheets of glossy baryta coated single weight paper at a rate of 700 sq. ft. per mol of silver. Two samples of each coating were exposed through a step wedge, developed, fixed and washed. One set of prints was dried without heat and the other set was dried on a ferrotype drum at to 200 F. The reflection D-max values obtained are tabulated below:
Dried Dried fg with heat A second series of experiments was performed in the same manner as the first except that different levels of potassium endothiophenylthiadiazoline thiol were used. The reflection D-max values obtained are tabulated below:
be as strong an antiplumming agent as the potassium salt, as the following will illustrate.
An emulsion was prepared according to Example 1 of U. S. Patent 2,596,756. To portions of this emulsion were added quantities of a 1:200 solution of endothiophenylthiadiazoline thiol dissolved in equal parts of methanol and acetone, and equivalent to 0, 0.5 and 2.0 g./mol of silver. These emulsions were then coated on glossy baryta-coated single-weight paper at a rate of 650 ft. mol of silver. Two samples of each coating were exposed through a step wedge, developed, fixed and washed. One set of prints was dried without heat, and the other Patented Apr.
These agents are employed preferably in 1 My invention is further illustrated in the following 'ex- 3 sets/as dried on a ferrotypedru'm at 180-200" F. The reflection D-max values obtained are tabulated below:
1 3 21 D a I'le 1'18 Without With Heat.
Heat
While inthis specification I have described my invention mainly 'with reference to the use of these anti-plumming agents in developing solutions and anti-plumming baths, my invention is not limited to such treatments.
adsorbed to the silver grains to give the desired anti-plumming effect during hotglazing of the print.
I claim:
1. The method'of preventing'image degradation of an exposed silver halide emulsion during drying which comprises performing at least one of the steps of developing,
. 4 fixing, washing and drying said emulsion in the presence of a compound having the formula:
2. A photographic silver halide emulsion containing from 0.1 and 4.0 grams per mol of silver halide of a compound having the formula:
oeH51 -N K- -s11 s 3. A photographic element containing a silver halide emulsion and from 0.2 and 7.0 milligrams per square foot of a compound having the formula:
References Cited in the file of this patent UNITED STATES PATENTS 2,353,754 Peterson July 18, 1944 FOREIGN PATENTS 471,339 Canada Feb. 6, 1951

Claims (1)

1. THE METHOD OF PREVENTING IMAGE DEGRADATION OF AN EXPOSED SILVER HALIDE EMULSION DURING DRYING WHICH COMPRISES PERFORMING AT LEAST ONE OF THE STEPS OF DEVELOPING, FIXING, WASHING AND DRYING SAID EMULSION IN THE PRESENCE OF A COMPOUND HAVING THE FORMULA:
US427373A 1954-05-03 1954-05-03 Photographic antiplumming agents and emulsions containing them Expired - Lifetime US2743184A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE537818D BE537818A (en) 1954-05-03
US427373A US2743184A (en) 1954-05-03 1954-05-03 Photographic antiplumming agents and emulsions containing them
GB12401/55A GB774618A (en) 1954-05-03 1955-04-29 Improvements in the production of photographic images
DEE10662A DE1005839B (en) 1954-05-03 1955-05-02 Process for preventing the image degradation of exposed halogen silver emulsions while they are drying
FR1123458D FR1123458A (en) 1954-05-03 1955-05-03 Photographic process and products to implement it

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US427373A US2743184A (en) 1954-05-03 1954-05-03 Photographic antiplumming agents and emulsions containing them

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US2743184A true US2743184A (en) 1956-04-24

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BE (1) BE537818A (en)
DE (1) DE1005839B (en)
FR (1) FR1123458A (en)
GB (1) GB774618A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3212892A (en) * 1960-07-27 1965-10-19 Agfa Ag Preventing darkening and formation of precipitates in solutions of photographic developers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1129907A (en) * 1965-10-11 1968-10-09 Agfa Gevaert Nv Photochemically cross-linkable polymers and compositions containing thiadiazole groups

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2353754A (en) * 1942-11-07 1944-07-18 Eastman Kodak Co Color photography using metallic salt coupler compounds
CA471339A (en) * 1951-02-06 Hampden Dimsdale Wilfrid Photographic light-sensitive elements

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA471339A (en) * 1951-02-06 Hampden Dimsdale Wilfrid Photographic light-sensitive elements
US2353754A (en) * 1942-11-07 1944-07-18 Eastman Kodak Co Color photography using metallic salt coupler compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3212892A (en) * 1960-07-27 1965-10-19 Agfa Ag Preventing darkening and formation of precipitates in solutions of photographic developers

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BE537818A (en)
FR1123458A (en) 1956-09-21
GB774618A (en) 1957-05-15
DE1005839B (en) 1957-04-04

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