US3446618A - Photographic silver halide emulsions containing trifluoromethyl - 4 - hydroxy quinoline carboxy acid salt as a stabilizer - Google Patents

Photographic silver halide emulsions containing trifluoromethyl - 4 - hydroxy quinoline carboxy acid salt as a stabilizer Download PDF

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Publication number
US3446618A
US3446618A US506840A US3446618DA US3446618A US 3446618 A US3446618 A US 3446618A US 506840 A US506840 A US 506840A US 3446618D A US3446618D A US 3446618DA US 3446618 A US3446618 A US 3446618A
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United States
Prior art keywords
silver halide
emulsion
stabilizer
quinoline
silver
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US506840A
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English (en)
Inventor
Fritz Dersch
Sally L Paniccia
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GAF Corp
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GAF Corp
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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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • 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

  • the present invention relates in general to the provision of novel additives for improving the sensitivity, contrast, covering power, etc. of photographic silver halide emulsions and in particular to the employment of certain quinoline derivatives for such purposes.
  • the sensitivity of light-sensitive silver halide emulsions can be increased in a number of ways as for example by the incorporation therein of one or more chemical or optical sensitizing agents which function to augment and/or extend the emulsion sensitivity to light of longer wave lengths.
  • chemical sensitization results from the formation of small amounts of silver sulfide and/or silver on the surface of the silver halide crystal.
  • compounds found to function as chemical sensitizing agents there may be mentioned sodium sulfite, sodium thiosulfate and the like.
  • covering power is a measure of the silver concentration in the developed image and is derived arithmetically by dividing the optical density at maximum density by the grams of silver per square decimeter in the developed image layer.
  • poly-N-vinyl lactams examples of materials heretofore promulgated for use as emulsion addenda to thereby obtain the requisite contrast, silvercovering power, etc.
  • the poly-N-vinyl lactams examples of materials heretofore promulgated for use as emulsion addenda to thereby obtain the requisite contrast, silvercovering power, etc.
  • the poly-N-vinyl lactams the watersoluble polyglucose dextrans, water-soluble S-hydroxyalkyl ethers of polyvinyl alcohol, water-soluble hydroiyzed glycogen, water-soluble mannan polysaccharide, the Water-soluble polyglucose laminarins, hydroxy-ethyl cellulose, carboxymethylated proteins and the like.
  • a primary object of the present invention resides in the provision of improved light-sensitive silver halide emulsions as well as photographic elements fabricated therewith in which the above and related disadvantages are eliminated or at least mitigated to a substantial extent.
  • a further object of the present invention resides in the provision of improved light-sensitive silver halide emulsions characterized by outstanding improvement in photographic speed, contrast and covering power of the silver image developed therein.
  • a still further object of the present invention resides in the provision of improved light-sensitive silver halide emulsion substantially devoid of any tendency to fog and further characterized by outstanding stability even under conditions of high temperature and/or humidity.
  • R represents hydrogen, lowr alkyl of l to 4 carbon atoms, e.g., methyl ethyl, propyl, etc. or a watersolubilizing cation, and R represents hydrogen or lower alkyl.
  • the phenylene nucleus in the above formula may further contain one or more inert substituents including for example, lower alkyl, lower alkoxy, e.g., methoxy, ethoxy, etc.; hydroxyalkyl, e.g., hydroxyethyl; halogen, e.g.. chloro, bromo, etc.
  • alkali metals e.g., sodium, potassium; ammonium; substituted ammonium, in which one or more of the hydrogens is replacedby lower alkyl, e.g., methyl, ethyl, propyl, etc.; hydroxy lower alkyl, e.g., hydroxy ethyl, and wherein such substituents may be the same or different.
  • silver halide emulsions of reduced fog, increased speed, contrast, and covering power of the developed silver can be obtained by including one or more of the compounds encompassed by the above formula in the light-sensitive silver halide layer, an undercoating, an intermediate coating, an overcoating and/or a surface coating.
  • concentrations employed are not particularly critical so long as sufficient amounts be present to impart to the emulsion the desired characteristics.
  • the quinoline derivative may be advantageously employed in concentrations varying over a relatively wide range and preferably from about 1 to about 40 milligrams per mole of silver halide.
  • ⁇ Vithin the aforesaid range, the amount selected will depend upon a variety of factors including for example the type of emulsion used. With emulsions of the high speed ammonia type, it is found that the use of 8 to milligrams of the above described quinoline derivative per mole of silver halide is particularly beneficial. Furthermore, in those embodiments wherein the quinoline compound is incorporated int-o a non-sensitized auxiliary layer, e.g., anti-abrasion layer, undercoating, etc., it is usually preferred that such quinoline derivative be utilized in the higher concentration range.
  • a non-sensitized auxiliary layer e.g., anti-abrasion layer, undercoating, etc.
  • the addition be made during the actual preparation of the emulsion, either before or after the emulsion washing step.
  • the improved anti-fogging and stabilizing elfects made possible by the present invention may also be obtained according to a further embodiment by including the quinoline derivative in the developer solution and/or alkaline pre-bath, i.e., such that the development'operation will be effected in the presence of such compound.
  • the quinoline derivative may be employed in concentrations ranging from about 1 to about 50 milligrams per liter of solution, with a range of about 5 to about milligrams per liter being particularly preferred.
  • quinoline derivatives encompassed by the abovedepicted structural formula are known compounds and are readily available commercially. Suitable methods for their preparation are described in standard reference works on the subject and in this connection particular reference is made to the procedures described in for example, J.A.C.S., 69, pp. 371-7-4 (1947) and I.A.C.S., 71, pp. 3507-08 (1949).
  • photographic elements prepared with the quinoline derivatives of the present invention are eminently suitable for such high speed machine processing in the virtual absence of fog, loss of speed, etc.
  • a silver halide emulsion in gelatin containing 4% silver iodide and 96% silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. It was then readied for coating on film base, that is, melted at 40 C.; necessary coating finals were added such as sensitizing dyes, stabilizers and hardeners. Approximately 8 cc. of a 0.1% solution of 3-carboxy-4-hydroxy-7-trifluoromethyl quinoline in methanol was added to a sample of the above-described emulsion containing about 0.6 mol of silver halide. A sample of the same emulsion, but not containing the quinoline compound served as a control. The so prepared emulsion samples were coated on a cellulose ester base and dried. Samples of these film coatings were then exposed in a Type IB Sensitometer and developed in a developer of the following composition:
  • EXAMPLE III The following example illustrates the improvements made possible by the present invention with photographic elements containing the novel quinoline additives when processed on high speed apparatus.
  • 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 as described in Example I. Test and control samples were prepared as in Example I. Following exposure in a Type IB Sensitometer, each of the samples was developed in an Eastman Kodak M4 X-Omat processing apparatus. The following results were obtained:
  • test samples (a), '(b), and (0) were sensitometrrcally exposed and developed in an M4 X-Omat apparatus (Eastman Kodak) with the following results:
  • the present invention is not limited to any particular type of light-sensitive silver halide as it is useful with silver chloride, silver bromide, silver iodo bromide, silver chloro bromide, silver iodide, etc., emulsions and mixed emulsions of these types. However, particularly beneficial results are obtained with silver halide emulsions containing on the order of at least mole percent silver bromide with the remainder silver iodide.
  • the improvements provided by the present invention are not dependent upon the use of any particular type of silver halide developer. Accordingly, the latter may be of the hydroquinone type, i.e., those which contain hydroquinone, potassium metabisulfite and potassium bromide, or they may be of the metol-hydroquinone type, i.e., those which contain p-methylaminophenol, sodium sulfite, sodium bisulfite, hydroquinone, sodium carbonate, and potassium bromide.
  • the developer composition may be of the so-called borax type, i.e., those which contain p-methylaminophenol sodium sulfite, hydroquinone, borax and potassium bromide.
  • the quinoline derivatives of the present invention may be employed singly or in combination with other sensitizing addenda including for example, the noble metal sensitizers, e.g., gold salts, e.g., chlorauric acid and auric trichloride and, if desired, in association with sulfur sensitizers, e.g., sodium sulfite, thiosinamine, allyl-thiourea, sodium thiosulfate, allyl thiocarbamate, alkali metal thiocyanates and sodium sulfide; these sensitizers can be used in amounts up to 0.005% based on the weight of the silver halide.
  • the silver halide emulsions may contain one or more optical sensitizing agents, e.g., cyanine, carbocyanine, merocyanine, pseudocyanine and other cyanine dyes.
  • the light-sensitive emulsions employed may be those of the type intended for use in color photography, e.g., emulsions containing color-forming components which upon color development with a primary aromatic amino developer yield azomethine quinonimine or azine dyes.
  • Suitable couplers are described in US. Patents 2,186,734, 2,445,252, 2,530,349, 2,671,021, 2,524,725, 2,354,552 and 2,547,037.
  • the color coupler may be of the non-diffusing type which, when added to the silver halide emulsion dispersed in a mixture of high boiling and low boiling solvent form packet-type emulsions with encapsulated color formers.
  • Suitable couplers of the latter type are described for example in US. Patents 2,179,239, 2,179,244, 2,298,443, 2,369,489 and 2,511,231.
  • a light-sensitive silver halide emulsion containing a stabilizer comprising from 1 to 40 mg. per mole of silver halide, of a compound of the following formula:
  • R is selected from the group consisting of hydrogen, lower alkyl and a water-solubilizing cation, and R is selected from the group consisting of hydrogen and lower alkyl.
  • a light-sensitive photographic material comprising a base and at least one light-sensitive silver halide emulsion, said photographic material containing a stabilizer com- COOR wherein R is selected from the group consisting of hydrogen, lower alkyl and a water-solubilizing cation and R is selected from the group consisting of hydrogen and lower alkyl.
  • a light-sensitive photographic material according to claim 4 wherein said stabilizer comprises 2-carboxy- 3-methyl-4-hydroxy-7-trifluoromethyl quinoline.
  • a process for the preparation of a photographic silver halide emulsion which comprises forming the emulsion, ripening the emulsion and during said ripening adding thereto a stabilizer comprising from 1 to 40 mg. per mol of silver halide of a compound of the following formula:
  • a process for the preparation of a photographic emulsion which comprises forming the emulsion, ripening the emulsion, coating said emulsion on a base and adding to said emulsion just prior to the coating thereof on the support a stabilizer comprising from 1 to 40 mg. per mol of silver halide, of a compound of the following formula:
  • R is selected from the group consisting of hydrogen, lower alkyl and a water-solubilizing cation, and R is selected from the group consisting of hydrogen and lower alkyl.

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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)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US506840A 1965-11-08 1965-11-08 Photographic silver halide emulsions containing trifluoromethyl - 4 - hydroxy quinoline carboxy acid salt as a stabilizer Expired - Lifetime US3446618A (en)

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US50684065A 1965-11-08 1965-11-08

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US (1) US3446618A (cs)
BE (1) BE689383A (cs)
DE (1) DE1547917A1 (cs)
FR (1) FR1498858A (cs)
GB (1) GB1130077A (cs)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4514492A (en) * 1983-12-15 1985-04-30 E. I. Du Pont De Nemours And Company Elimination of defects in cysteine-sensitized emulsions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2397015A (en) * 1943-02-12 1946-03-19 Ilford Ltd Silver halide photographic emulsions
US2578655A (en) * 1948-05-08 1951-12-18 Ilford Ltd Photographic silver halide emulsions containing 4-hydroxy quinolines
US2948615A (en) * 1958-03-13 1960-08-09 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US3193386A (en) * 1961-11-29 1965-07-06 Du Pont Silver halide emulsions and elements containing antifoggants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2397015A (en) * 1943-02-12 1946-03-19 Ilford Ltd Silver halide photographic emulsions
US2578655A (en) * 1948-05-08 1951-12-18 Ilford Ltd Photographic silver halide emulsions containing 4-hydroxy quinolines
US2948615A (en) * 1958-03-13 1960-08-09 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
US3193386A (en) * 1961-11-29 1965-07-06 Du Pont Silver halide emulsions and elements containing antifoggants

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4514492A (en) * 1983-12-15 1985-04-30 E. I. Du Pont De Nemours And Company Elimination of defects in cysteine-sensitized emulsions
EP0145506A3 (en) * 1983-12-15 1986-01-22 E.I. Du Pont De Nemours And Company Elminination of defects in cysteine-sensitized emulsions

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Publication number Publication date
DE1547917A1 (de) 1969-12-11
BE689383A (cs) 1967-04-14
GB1130077A (en) 1968-10-09
FR1498858A (fr) 1967-10-20

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