US3193386A - Silver halide emulsions and elements containing antifoggants - Google Patents

Silver halide emulsions and elements containing antifoggants Download PDF

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Publication number
US3193386A
US3193386A US155852A US15585261A US3193386A US 3193386 A US3193386 A US 3193386A US 155852 A US155852 A US 155852A US 15585261 A US15585261 A US 15585261A US 3193386 A US3193386 A US 3193386A
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US
United States
Prior art keywords
silver halide
hydroxyquinoline
grams
emulsion
silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US155852A
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English (en)
Inventor
Clayton F A White
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EIDP Inc
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EI Du Pont de Nemours and Co
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Filing date
Publication date
Priority to BE625436D priority Critical patent/BE625436A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US155852A priority patent/US3193386A/en
Priority to GB45038/62A priority patent/GB984381A/en
Priority to FR916907A priority patent/FR1339990A/fr
Priority to DEP30667A priority patent/DE1158831B/de
Application granted granted Critical
Publication of US3193386A publication Critical patent/US3193386A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • G03C1/36—Desensitisers
    • 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

  • Light-sensitive silver halide emulsion coated elements are used in the graphic arts industry for the production of lithographic and letterpress plates. These elements must be very stable sensitometrically and should be highly resistant to safelight fog. This is because in high quality Work, technicians closely examine the films during development, with the aid of strong safelight illumination, to determine when to terminate development for optimum halftone dot quality. This visual inspection may take place while the film is in the developing solution or when the film is taken out of the developer and held up to the safelight. This places a premium on light-sensitive elements for graphic arts use which have a maximum tolerance for safelight illumination during development.
  • Photographic emulsions for lithographic purpose are usually composed of silver bromochloride grains predominating in silver chloride which are particularly sus ceptible to safelight fogging when a conventional halftone paraformaldehyde-hydroquinone type developer is used.
  • the improved silver halide emulsions and emulsion layers of this invention are colloid silver halide emulsions predominating in silver chloride and contain a mixture of about 0.15 to about 2.50 grams of unsubstituted 8-hydroxyquinoline and about 0.40 to about 2.40 grams of 8- hydroxyquinoline--sulfonic acid per mol of silver halide.
  • the colloid preferably is gelatin.
  • Improved lithographic film elements of the invention comprise a colloid silver halide emulsion layer predominating in silver chloride and having in intimate association with the silver halide grains of such layer a mixture of 0.15 to about 2.50 grams of unsubstituted 8-hydroxyquinoline and about 0.40 to about 2.40 grams of S-hydroxyquinoline-5-sultonic acid per mol of silver halide.
  • the mixture of quinoline compounds are preferably in the silver halide emulsion layer but may be present in a water-permeable sublayer or overcoating. When used in contiguous layers, it is preferable to use of the order 3,l3,330 Patented July 6, 1965 ice of from 2 to 4 times the quantities of the two 8-hydroxyquinoline compounds used in the emulsion layer.
  • the mixture of the two S-hydroxyquinoline compounds is very efiective in preventing safelight fog due to the presence of the unsubstituted 8-hydroxyquinoline compound, and because of the presence of the 5-sulfonic acid derivative is also stabilized against the formation of development fog, especially when metol-hydroquinone developers are used.
  • the invention is not limited to gelatin silver halide emulsions containing only gelatin as the sole silver halide binding agent since emulsions containing such agents as polyvinyl pyrrolidone, dextrin, dextrans and/or other such agents which increase silver covering power can be present in the gelatin silver halide emulsions. Also, conventional emulsion adjuvants can be present and they are not atfected by the S-hydroxyquinoline compounds.
  • the invention is equally efiective in both orthochromatically sensitized and non-optically sensitized photographic gelatino-silver halide emulsions.
  • non-optical sensitizers there may be mentioned sulfur sensitizers containing labile sulfur, e.g., allyl isothiocyanate, allyl diethyl thiourea, phenyl isothiocyanate and sodium thiosulfate; the polyoxyalkylene ethers disclosed in Blake et al. U.S. Patent 2,400,532, and the polyglycols disclosed in Blake et al. U.S. 2,423,549.
  • the amines as disclosed in Staud et al. U.S. 1,925,508 and the metal salts disclosed in Baldsiefen U.S. 2,540,085 and Baldsiefen et al. 2,540,086 may also be used.
  • Antifoggants which can be used in the emulsions of this invention include benzotriazole and triazaindenes; the emulsions, moreover, may contain the usual hardeners, i.e., chrome alum, formaldehyde, etc.
  • Other emulsion adjuvants well known in the art may be added, e.g., matting agents, plasticizers, toners, optical brightening agents, etc.
  • the emulsions of the invention may be coated on any suitable support, e.g., cellulose esters, cellulose mixed esters; super-polymers, e.g., polyvinyl chloride (co) vinyl acetate, polyvinyl acetals, e.g., formals, acetals, polystyrene, polyamides, e.g., polyhexamethylene adipamide, and polyesters, e.g., polycarbonates, polyethylene terephthalate, polyethylene terephathalate/isophthalate, esters formed by condensing terephthalic acid and dimethyl terephthalate with propylene glycol, diethylene glycol, tetramethylene glycol or cyelohexane-1,4-dimethanol (he-xahydro-p-xylene alcohol).
  • gelatin binding agents used in the following examples, there can be substituted other natural or synthetic water-permeable organic colloid binding agents.
  • Such agents include water-soluble or permeable polyvinyl alcohol and its derivatives, e.g., partially hydrolyzed polyvinyl acetates, polyvinyl ethers, and acetals containing a large number of intralinear -CH CHOH groups; hydrolyzed interpolymers of vinyl acetate and un saturated addition polymerizable compounds such as maleic anhydride, acrylic and methacrylic acid ethyl esters, and styrene.
  • Suitable colloids of the last mentioned type are disclosed in U.S.
  • Patents 2,276,322; 2,276,323; and 2,397,866 Useful polyvinyl acetals include polyvinyl acetaldehyde acetal, polyvinyl butyraldehyde acetal and polyvinyl sodium o-sulfobenzaldehyde acetal.
  • Other useful colloid binding agents include the poly-N-vinyllactams of Bolton U.S. Patent 2,495,918, the hydrophilic copolymers of N-acrylamido alkyl betaines described in Shacklett U.S. Patent 2,833,650, and hydrophilic cellulose ethers and esters.
  • EXAMPLE I A lithographic emulsion having a silver halide composition of 30 mole percent silver bromide and 70 mole percent silver chloride and having 20 grams of gelatin present per mole of silver halide for the steps of precipitation and ripening was freed of unwanted, soluble by-.
  • Part 1 No further additions were made and this part served as a control.
  • Part 3 To this part there was added 33.3 ml. of a solution prepared bydissolving 12.0 grams of 8-hydroxyquinoline in one liter of ethyl alcohol. This provides 0.40 gram of the compound per mol of silver halide.
  • Part 4 To this portion there were added both 8-hydroxyquinoline-S-sulfonic acid and 8-hydroxyquinoline in the same quantities per mol of silver halide as added in parts two and three respectively.
  • Procedure A During this development the films were exposed to a Wratten 1-A red safelight illuminated with a 60-wat-t tungsten filament lamp operated at volts which was positioned 30 inches above the developing tray to permit easy inspection of the image during the development. Ordinarily the typical procedure in commercial practice does not comprise developing for any set time but for,
  • a period sufiicient to providethe quality of halftone image desired in terms of halftone dotsize and density is ascertained by visual inspection.
  • the four minute interval used here is close to, or above, the maximum period of development for lithographic films and for practical purposes, far above the developing time usually used.
  • the procedure here is for the purpose of demonstrating the ability of S-hydroxyquinoline to control fog caused by strong safelight illumination and to show the ineffectiveness of 8-hydroxyquinoline 5-sulfonic acid for this pur- After development, the films were treated in a conventional hardening fixing bath, washed and dried. The sensitometric results were readon a conventional densitometer and the net fog densities are shown in the table below.
  • Safelight illumination during this development was of the same spectral transmission as in Procedure A but of a low intensity.
  • the safelight consisted of a l5-watt lamp screened by a Wratten lA filter positioned eight feet from the development tray which is typical of the practice where close visual inspection is not used or required.
  • the practice is used for copywork and high volume reproduction black and white work where the high quality halftone negatives used for color work, etc. are not required.
  • a set, predetermined development time is used.
  • 'Fog resulting from these conditions is of the chemical type resulting from the use of metol-hydroquinone high energy developers.
  • the films were fixed, Washed and dried as in Procedure A. Net fog density readings resulting from the above processing is shown in the table below along with the results of Procedure A,
  • film sample number four has excellent resistance to both high intensity safelight illumination and chemical fog caused by high energy developers.
  • Example II Example I was repeated and the emulsion was divided into five equal portions and additions of 8 hydroxyquinoline and 8-hydroxyquinoline-5-sulfonic acid were made as shown in the following table.
  • the emulsions were coated on film base support, dried, overcoated, etc., as described in Example I.
  • Fog Test Fog Test, Sample Procedure A.
  • Procedure B Net Fog Net Fog
  • a further advantage of the invention is that the presence of S-hydroxyquinoline also provides a high degree of immunity against many spot-forming, trace contaminants which may be found within the silver halide emulsion or which may come in contact with the surface of the coated film prior to development.
  • the tendency of commercial lithographic films to form intensified spots when in contact with the smoke (or dust) from carbon arc lamps in a typical process camera darkroom is overcome by the novel emulsions and lithographic film elements of this invention.
  • a photographic element comprising a support and a layer of a colloid-silver halide emulsion predominating in silver chloride and containing a mixture of about 0.15 to about 2.50 grams of unsubstituted S-hydroxyquinoline and about 0.40 to about 2.40 grams of B-hydr-oxyquinoline- 5-sulfonic acid per mole of silver halide.
  • a photographic element comprising a film support and a layer of a colloid-silver halide emulsion predominating in silver chloride and containing a mixture of about 0.15 to about 2.50 grams of unsubstituted 8-hydroxyqu noline and about 0.40 to about 2.40 gramsof S-hydroxyquinoline-5-sulfonic acid per mole of silver halide.
  • a photographic element comprising a film support and a layer of a gelatino-silver halide emulsion predominating in silver chloride and containing a mixture of about 0.15 to about 2.50 grams of unsubstituted 8-hydroxyquin-oline and about 0.40 to about 2.40 grams of 8-hydroxyquinol-ine-S-sulfonic acid per mole of silver halide.
  • a photographic element comprising a film support and a layer of a gelatino-silver bromochloride emulsion predominating in silver chloride and containing a mixture of about 0.15 to about 2.50 grams of unsubstituted 8-hydroxyquinoline and about 0.40 to about 2.40 grams of S-hydroxyquinoline-S-sulfonic acid per mole of silver halide.

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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)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Colloid Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US155852A 1961-11-29 1961-11-29 Silver halide emulsions and elements containing antifoggants Expired - Lifetime US3193386A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE625436D BE625436A (de) 1961-11-29
US155852A US3193386A (en) 1961-11-29 1961-11-29 Silver halide emulsions and elements containing antifoggants
GB45038/62A GB984381A (en) 1961-11-29 1962-11-28 Improvements in silver halide emulsions
FR916907A FR1339990A (fr) 1961-11-29 1962-11-28 émulsions d'halogénure d'argent et d'un colloïde
DEP30667A DE1158831B (de) 1961-11-29 1962-11-28 Photographische Halogensilberemulsion mit Kolloiden als Bindemittel und mit ueberwiegendem Gehalt an Chlorsilber, insbesondere auf Traegern, wie Filmen

Applications Claiming Priority (1)

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US155852A US3193386A (en) 1961-11-29 1961-11-29 Silver halide emulsions and elements containing antifoggants

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US3193386A true US3193386A (en) 1965-07-06

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US (1) US3193386A (de)
BE (1) BE625436A (de)
DE (1) DE1158831B (de)
FR (1) FR1339990A (de)
GB (1) GB984381A (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3272628A (en) * 1963-12-17 1966-09-13 Eastman Kodak Co "lith" developers containing water soluble block polymers of polyoxypropylene and polyoxyethylene
US3294540A (en) * 1963-12-17 1966-12-27 Eastman Kodak Co Lith-type emulsions with block co-polymers
US3446618A (en) * 1965-11-08 1969-05-27 Gaf Corp Photographic silver halide emulsions containing trifluoromethyl - 4 - hydroxy quinoline carboxy acid salt as a stabilizer
FR2156199A1 (de) * 1971-10-11 1973-05-25 Fuji Photo Film Co Ltd
US4520099A (en) * 1982-09-02 1985-05-28 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US4965184A (en) * 1989-02-23 1990-10-23 E. I. Du Pont De Nemours And Company Silver halide emulsions with improved speed
US5340695A (en) * 1992-08-25 1994-08-23 Fuji Photo Film Co., Ltd. Silver halide photographic materials
EP0694810A1 (de) * 1994-07-27 1996-01-31 Eastman Kodak Company Eine neue Klasse von Kornwachstumsmodifikatoren zur Herstellung tafelförmiger Emulsionen mit hohem Chlorid (III)
EP0697619A2 (de) 1994-08-17 1996-02-21 Eastman Kodak Company Photographische Hochkontrastelemente mit verbesserter Maximaldichte
EP0774686A2 (de) 1995-11-14 1997-05-21 Eastman Kodak Company Photopgraphische Hochkontrastmaterialien geschützt gegen Aufhelleffekte

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2691588A (en) * 1952-03-14 1954-10-12 Eastman Kodak Co Photographic developers containing 8-hydroxyquinolines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2691588A (en) * 1952-03-14 1954-10-12 Eastman Kodak Co Photographic developers containing 8-hydroxyquinolines

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3272628A (en) * 1963-12-17 1966-09-13 Eastman Kodak Co "lith" developers containing water soluble block polymers of polyoxypropylene and polyoxyethylene
US3294540A (en) * 1963-12-17 1966-12-27 Eastman Kodak Co Lith-type emulsions with block co-polymers
US3446618A (en) * 1965-11-08 1969-05-27 Gaf Corp Photographic silver halide emulsions containing trifluoromethyl - 4 - hydroxy quinoline carboxy acid salt as a stabilizer
FR2156199A1 (de) * 1971-10-11 1973-05-25 Fuji Photo Film Co Ltd
US4520099A (en) * 1982-09-02 1985-05-28 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US4965184A (en) * 1989-02-23 1990-10-23 E. I. Du Pont De Nemours And Company Silver halide emulsions with improved speed
US5340695A (en) * 1992-08-25 1994-08-23 Fuji Photo Film Co., Ltd. Silver halide photographic materials
EP0694810A1 (de) * 1994-07-27 1996-01-31 Eastman Kodak Company Eine neue Klasse von Kornwachstumsmodifikatoren zur Herstellung tafelförmiger Emulsionen mit hohem Chlorid (III)
EP0697619A2 (de) 1994-08-17 1996-02-21 Eastman Kodak Company Photographische Hochkontrastelemente mit verbesserter Maximaldichte
EP0774686A2 (de) 1995-11-14 1997-05-21 Eastman Kodak Company Photopgraphische Hochkontrastmaterialien geschützt gegen Aufhelleffekte

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Publication number Publication date
FR1339990A (fr) 1963-10-11
GB984381A (en) 1965-02-24
DE1158831B (de) 1963-12-05
BE625436A (de)

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