US3512982A - Nucleic acids as fog stabilizers for photographic emulsions - Google Patents

Nucleic acids as fog stabilizers for photographic emulsions Download PDF

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Publication number
US3512982A
US3512982A US628830A US3512982DA US3512982A US 3512982 A US3512982 A US 3512982A US 628830 A US628830 A US 628830A US 3512982D A US3512982D A US 3512982DA US 3512982 A US3512982 A US 3512982A
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Prior art keywords
silver halide
fog
silver
photographic
emulsion
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US628830A
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English (en)
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Robert C Taber
William H Russell
Charles A Goffe
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/496—Binder-free compositions, e.g. evaporated
    • G03C1/4965—Binder-free compositions, e.g. evaporated evaporated
    • 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

Definitions

  • This invention relates to new and improved antifoggants and stabilizers for photographic elements and to photographic silver halide emulsions containing said antifoggants and stabilizers therein.
  • the invention also relates to a process of developing photographic elements in the presence of new and improved antifoggants.
  • emulsion stabilizers and antifoggants have been used in the prior art, many of these compounds cause undesirable losses in emulsion speed and contrast and others lack adequate compatibility with emulsion gelatin.
  • Some addenda which have been used in the past to control extended development fog have the disadvantage of attacking the latent image. For example, mercuric chloride added to a photographic emulsion controls fog but results in loss of density if the exposed film is not processed soon after exposure.
  • a fog-stabilizing amount of a nucleic acid there is incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion, a fog-stabilizing amount of a nucleic acid.
  • the nucleic acid stabilizes the emulsion against fog when Patented May 19, 1970 ice DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the nucleic acid may be incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion in any amount which will stabilize the silver halide emulsion against fog.
  • a concentration of the nucleic acid in an amount of from about 0.025 to about 10, preferably about 0.050 to about 2, grams per mole of silver in the silver halide emulsion can be used with good results.
  • Nucleic acids are made up of three components, liberated on acid hydrolysis: an organic base or bases, phosphoric acid and a sugar.
  • the sugar unit is either ribose or 2-deoxyribose.
  • Both deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) contain the bases adenine, guanine and cytosine.
  • DNA deoxyribonucleic acid
  • RNA ribonucleic acid
  • DNA the fourth base is thymine while in RNA the fourth base is uracil.
  • DNA alone, RNA alone or mixtures of DNA and RNA can be employed.
  • the preparation of photographic silver halide emulsions such as are suitably stabilized with a nucleic acid typically involves three separate operations: (1) emulsification and digestion of silver halide, (2) the freeing of the emulsion of excess Water-soluble salts, suitably by washing with water, and (3) the second digestion or after-ripening to obtain increased emulsion speed or sensitivity.
  • the nucleic acid can be added to the emulsion before the final digestion or after-ripening or it can be added immediately prior to the coating.
  • the silver halide emulsion of a photographic element containing the antifoggants of this invention can contain conventional addenda such as gelatin plasticizers, coating aids, antifoggants such as the azaindines and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.
  • aldehyde hardeners e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.
  • Sensitizing dyes useful in sensitizing such emulsions are described, for example, in US. Pats. 2,526,632 of Brooker and White issued Oct.
  • Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.
  • Developing agents can also be incorporated into the silver halide emulsion if desired or can be contained in a separate underlayer.
  • Various silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • the silver halide emulsion layer of a photographic element containing the antifoggants of the invention can contain any of the hydrophilic, water-permeable binding materials suitable for this purpose. Suitable materials include gelatin, colloidal albumin, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc. Mixtures of these binding agents can also be used.
  • the binding agents for the emulsion layer of the photographic element can also contain dispersed polymerized vinyl compounds. Such compounds are disclosed, for example, in US. Pats. 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of White issued July 6, 1965; 3,062,674 of 3 Houck, Smith and Yudelson issued Nov.
  • Typical supports are cellulight-sensitive layer to a second layer, while the two laylose nitrate film, cellulose ester film, polyvinyl acetal film, ers are in close proximity to one another.
  • the antifoggants could also be utilized coated with a-olefin polymers, particularly polymers of by incorporating them into a photographic developer, a-olefins containing two or more carbon atoms, as exemsince image formation would still take place in the presplified by polyethylene, polypropylene, ethylene-butene ence of the antifoggants and they would still perform their copolymers and the like can also be employed. antifoggant function.
  • the speed of the photographic emulsions containing The antifogging agents of this invention can be inthe antifoggants of the invention can be further increased corporated to advantage during manufacture in silver by including in the emulsions a variety of hydrophilic colhalide emulsions representing the variations described loids such as carboxymethyl protein of the type described above.
  • fog control in binderless silver halide in US. Pat. 3,011,890 of Gates, Jr., Miller and Koller films prepared by vapor deposition of silver halide on 21 issued Dec. 5, 1961, and polysaccharides of the type desuitable support can be achieved by coating the antiscribed in Canadian Pat. 635,206 of Koller and Russell fogging agents of the invention over the vapor deposited issued J an. 23, 1962. layer of silver halide.
  • Photographic emulsions containing the antifoggants of 25 The invention can be further illustrated by the followthe instant invention can also contain speed-increasing ing examples or preferred embodiments thereof; although compounds such as quaternary ammonium compounds, it will be understood that these examples are included polyethylene glycols or thioethers. Frequently, useful efmerely for purposes of illustration and are not intended fects can be obtained by adding the aforementioned speedto limit the scope of the invention. increasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emul- EXAMPLE 1 sions.
  • Photographic elements containing the antifoggants of containing, respectively, no antifoggant, HgCl and vary the invention can be used in various kinds of photoing amounts of RNA are ripened to optimum sensitivity graphic systems.
  • they can also be erage of 478 milligrams of silver per square foot and 474 used in orthochromatic, panchromatic and infrared sensimilligrams of gelatin per square foot.
  • the sensitizing addenda can be added to coatings is exposed for 10* second on an intensity scale photographic systems before or after any sensitizing dyes sensitometer, processed for three minutes in Kodak D-19 which are used. Developer containing 10 milligrams of potassium iodide Silver halide emulsions containing the antifoggants of per liter, fixed, washed and dried. The procedure is rethe invention can be used in color photography, for expeated with a second set of film coatings except that the ample, emulsions containing color-forming couplers or film coating is processed for eight minutes in the deemulsions to be developed by solutions containing couveloper.
  • a third set of film coatings exposed three days plers or other color-generating materials, emulsions of the 5 earlier and kept at 78 F. is processed for three minutes mixed-packet type such as described in US. Pat. 2,698,794 in the developer, fixed, washed and dried.
  • the photoof Godowsky issued Jan. 4, 1955; in silver dye-bleach graphic results obtained from these tests are set forth systems; and emulsions of the mixed-grain type such as in Table I.
  • D is the loss in density of film described in US. Pat. 2,592,243 of Carroll and Henson coatings which have been kept at 7 8 F. for three days issued Apr. 8, 1952. after an exposure which produces a fresh density of 1.0;
  • Silver halide emulsions containing the antifoggants of and D is the loss in density of film coatings which have the invention can be sensitized using any of the wellbeen kept at 78 F. for three days after an exposure known techniques in emulsion making, for example, by which produces a fresh density of 2.0.
  • the emulsions can also be sensitized with salts of noble metals of Group VIII of the Periodic Table which have an atomic Weight greater than 100.
  • RNA as an antifoggant in a high speed silver halide emulsion of the type receiving layer in close proximity to the original silver used in medical X-ray films.
  • the coatings are given a 5 second simulated blue screen exposure and processed for six minutes in Kodak D-l9 Developer containing 10 milligrams of potassium iodide per liter.
  • the photographic results obtained from these tests are set forth in Table II.
  • EXAMPLE 3 A silver bromoiodide emulsion is prepared corresponding to Emulsion No. 12 described in Empirical Relations Between Sensitometric and Size-Frequency Characteristics in Photographic Emulsion Series by Trivelli and Smith, Photo. Journal, May 1939, page 330. Two samples of this emulsion, one (the control) containing no antifoggant and the other containing 1.0 gram of RNA per mole of silver, are coated on a cellulose acetate film support at a coverage of 450 milligrams of silver and 1030 milligrams of gelatin per square foot. A sample of each film coating is exposed for second on an intensity scale sensitometer, processed for five minutes in Kodak Developer DK- 50, fixed, washed and dried. The photographic results obtained are listed in Table III.
  • a composition comprising a photographic silver halide emulsion containing a fog-stabilizing amount of ribonucleic acid or deoxyribonucleic acid.
  • a photographic element comprising a support coated with a silver halide layer, said element containing a fog-stabilizing amount of ribonucleic acid or deoxyribonucleic acid.
  • nucleic acid ribonucleic acid or deoxyribonucleic acid
  • said nucleic acid, ribonucleic acid or deoxyribonucleic acid is present in an amount of from about 0.025 to about 10 grams per mole of silver in said silver halide emulsion.
  • nucleic acid ribonucleic acid or deoxyribonucleic acid
  • nucleic acid is present in a layer contiguous to said silver halide emulsion.
  • composition of claim 1 containing a fogstahilizing amount of ribonucleic acid.
  • the photographic element of claim 3 containing a fog-stabilizing amount of ribonucleic acid.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US628830A 1967-04-06 1967-04-06 Nucleic acids as fog stabilizers for photographic emulsions Expired - Lifetime US3512982A (en)

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BE (1) BE712835A (en:Method)
FR (1) FR1559408A (en:Method)
GB (1) GB1195608A (en:Method)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3982948A (en) * 1973-07-02 1976-09-28 Konishiroku Photo Co. Ltd. Process for preparing silver halide emulsion containing a rhodium salt and a decomposition product of nucleic acid

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2296204A1 (fr) * 1974-12-27 1976-07-23 Kodak Pathe Nouvelles emulsions negatives aux halogenures d'argent protegees contre la desensibilisation par pression

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3023103A (en) * 1960-08-02 1962-02-27 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US3148066A (en) * 1961-06-29 1964-09-08 Eastman Kodak Co Nitramino and nitrosamino compounds as antifoggants for photographic emulsions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3023103A (en) * 1960-08-02 1962-02-27 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US3148066A (en) * 1961-06-29 1964-09-08 Eastman Kodak Co Nitramino and nitrosamino compounds as antifoggants for photographic emulsions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3982948A (en) * 1973-07-02 1976-09-28 Konishiroku Photo Co. Ltd. Process for preparing silver halide emulsion containing a rhodium salt and a decomposition product of nucleic acid

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BE712835A (en:Method) 1968-07-31
FR1559408A (en:Method) 1969-03-07

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