US3520694A - Gelatin-silver halide compositions containing trihydric alcohols - Google Patents

Gelatin-silver halide compositions containing trihydric alcohols Download PDF

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Publication number
US3520694A
US3520694A US602150A US3520694DA US3520694A US 3520694 A US3520694 A US 3520694A US 602150 A US602150 A US 602150A US 3520694D A US3520694D A US 3520694DA US 3520694 A US3520694 A US 3520694A
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United States
Prior art keywords
silver halide
gelatin
compound
emulsion
photographic
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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
Application number
US602150A
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English (en)
Inventor
Fumihiko Nishio
Nobuo Yamamoto
Hideo Kawano
Hiroshi Onishi
Masaji Yoshida
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
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Publication of US3520694A publication Critical patent/US3520694A/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives

Definitions

  • the present invention relates to a photographic gelatino silver halide light-sensitive element.
  • a gelatino silver halide emulsion coating on a natural or synthetic polymer support such as paper, a cellulose ester, or a polyester is usually reduced in flexibility and other physical properties under the conditions of low temperature and low humidity. Additionally, if a mechanical stress such as tortion, bending or friction is added thereto during manufacturing or during processing after manufacture before development, it is sometimes endowed with undesirable photographic properties such as desensitization, fogging and the like. Furthermore, it is commonly known that in the case of employing a so-called Festoon-drying system to dry a gelatino silver halide emulsion coating, an undesirable annular ring like pattern, so-called stick mark, appears at the portion which was dried unevenly, caused by being placed in an intermittent drying condition (cf. e.g., E. Ziind; Zeitchrift fur Schmchaftliche photographic photophysic und photochemie, vol. 49, pages 25403).
  • an object of the prevent invention is to provide a photographic gelatino silver halide light-sensitive material in which the physical properties and the adhesive property of the emulsion layer to the support are not reduced, the formations of darking, desensitization caused by strain, stick mark as mentioned above ice are restrained, the stickiness of the gelatin coating to other surfaces is weak, and the preservation properties thereof are good.
  • R represents an alkyl group having from 1 to 5 carbon atoms.
  • the compound may usually be prepared by the reaction of aliphatic aldehyde such as propionaldehyde or n-butylaldehyde with formaldehyde.
  • the amount of the compound added to the phot graphic material in this invention is not particularly limited but l30% by weight to the amount of gelatin is preferable. That is, if the amount is less than 1% by weight, a remarkable effect is not obtained, and if it is larger than 30% by weight, the coated layer becomes stickly. In particular, if the amount of the compound added is 5-20% by weight to the amount of gelatin, the desensitization and draking caused by strain of the gelatino silver halide layer containing the compound by mechanical stress and the formation of stick mark thereof by uneven drying are markedly restrained. Furthermore, the stickiness of the surface of the coating is remarkably improved as compared with the case of adding a known plasticizer.
  • the compound of this invention may be dissolved in a solvent which has no detrimental effect on the photographic silver halide emulsion; such a solvent might be water, lower alcohol such as methanol ethanol and the like, or ketone such as acetone.
  • a solvent might be water, lower alcohol such as methanol ethanol and the like, or ketone such as acetone.
  • the compound may then be added to the photographic gelatin silver halide emulsion at any stage before coating. However, it is most preferable to add after second ripening and before coatmg.
  • the trihydric alcohols of this invention may be incorporated in other gelatin-coating composition, for example, a protective layer and intermediate layer of a photographic light-sensitive material, and also may be incorporated in a photographic gelatino silver halide emulsion and other gelatin-containing coating composition simultaneously.
  • the photographic gelatino silver halide emulsions to be employed in this invention may be emulsions for black and white positive or negative photographic light-sensitive material and/or light-sensitive graphic art material, emulsions for photographic X-ray film, and coupler-inemulsion type color photographic emulsion wherein a color coupler is incorporated in the emulsion, and coupler-in-developer type color photographic emulsion wherein a color coupler is incorporated in a developer.
  • the compound of this invention may be incorporated with a good result in various silver halide emulsions, such as, a silver chloride emulsion, and silver bromide emulsion, and silver bromo-chloride emulsion and a silver bromo-iodide emulsion, and the like.
  • the silver halide emulsion to be used in this invention may be chemically sensitized by a conventional method, for example, with a compound containing unstable sulfur, such as ammonium thiosulfate or allylthiourea (for example, P. Glafkides; Chimie photographique; 2 eme edition, publication photocinema, Paul Montel Peris, pages 297-299, 1957), a complex salts of mono-valent gold and thiocyanic acid (cf. ibid., page 301), a polyalkylene oxide derivative, or a combination thereof.
  • a compound containing unstable sulfur such as ammonium thiosulfate or allylthiourea (for example, P. Glafkides; Chimie photographique; 2 eme edition, publication photocinema, Paul Montel Peris, pages 297-299, 1957), a complex salts of mono-valent gold and thiocyanic acid (cf. ibid., page 301), a polyalkylene
  • the silver halide emulsion or other gelatin-containing coating composition to be employed in this invention may further contain a well-known wetting agent, such as nonionic, anionic and amphoteric surface active agents (e.g. polyoxyethylene nonylphenyl ether, sodium alkylbenzene sulfonate, or N-methylalkyl tauride) and anionic surface active agents containing an ethylene oxide chain as described in Belgian Pat. 650,004.
  • a wetting agent such as nonionic, anionic and amphoteric surface active agents (e.g. polyoxyethylene nonylphenyl ether, sodium alkylbenzene sulfonate, or N-methylalkyl tauride) and anionic surface active agents containing an ethylene oxide chain as described in Belgian Pat. 650,004.
  • nonionic, anionic and amphoteric surface active agents e.g. polyoxyethylene nonylphenyl ether, sodium alkylbenzene sulfonate, or N-
  • EXAMPLE 1 An aqueous 20% solution of trimethylolethane (Compound 1) or trimethylolpropane (Compound 2) was added in a negative high-sensitive silver bromo-iodide emulsion containing 7% by weight of gelatin which had been sensitized with sulfur and gold. The resulting emulsion was applied to a cellulose triacetate base so that the dried thickness of the coating after drying was 10:1 microns. Then, the coated layer was set by supplying the clear air of 7 C. and then dried for about 50 minutes by passing the thus coated film through a drying chamber in which the drying temperature was so controlled that it was raised gradually from 18 C. to 45 C. A sample of 5 cm. x 12 cm.
  • N-methyl-p-aminophenol sulfate 1.0 Sodium sulfite (anhydrous) 75.0 Hydroquinone 9.0 Sodium carbonate mono-hydrate 30.0 Potassium bromide .4... 5.0
  • the developed coatings were fixed, water-washed and dried as usual, and then the density of the portion blackened by the pressure was measured.
  • the above-prepared film was placed for 48 hours in an atmosphere of 85% in relative humidity at 35 C. Then, the film was folded so that the emulsion layers were in contact with each other; it was allowed to stand for 24 hours in the same atmosphere while adding the static pressure of 50 g./ sq. cm., and then the sticked areas of the emulsion layer were measured.
  • the coated layer was set by supplying clear air of 7 C., and dried for about 40 minutes by passing the thus coated film through a, drying chamber in which the drying temperature was so controlled that it was raised gradually from 18 C. to 35 C.
  • a sample was cut off from the film, subjected to above conditioned atmosphere, folded and pressed as in Example 1.
  • the sample was exposed such that the optical density thereof after development would become about 1.0, developed for 3 minutes at 20 C. in the developer having the following composition:
  • the sample was then subjected to fixing, water-washing and drying as usual, and the difference between the density of the portion of which the sensitivity was reduced by the pressure and the density of the non-pressed portion was measured. Apart from this, the film was also treated by the process as in Example 1 and the sticked areas were measured.
  • Quantity (g./100 g. Density sticked Compound gelatin) difference area, percent Compound 2 6. 5 0. 30 45 D 13.0 0.15 50 6.5 0.35 40 13.0 0.15 50 6.5 0. 40 700 13.0 0.25 None 0.60 40 EXAMPLE 3
  • a 20% aqueous solution containing trimethylol propane (Compound 2) or trimethylol hexane (Compound 4) was added into a silver bromo-iodide negative emulsion of a high ratio of silver to gelatin containing 7% by weight of gelatin, which had been sensitized with sulfur and gold, and the resulting emulsion was applied to a polyethylene terephthalate base so that the dried thickness of the coating was 10:1 microns.
  • the coated layer was set by supplying clear air of 7 C.
  • a sample of 20 cm. x 20 cm. in area was cut off from the film and placed on a horizontally placed flat plate such that the uncoated side of the film was in contact with the plate.
  • air of about 2325 C. was uniformly supplied onto the surface to dry it so that the water-content became 55:5%, and thereafter air of 35 C. in temperature and 50:5% in relative humidity was supplied to the film for 30 seconds through a nozzle having an inside diameter of 1.5 cm. placed above the sample at a distance of 20 cm.
  • the air supply was interrupted for 1 minute, and was repeated until the whole surface of the coated layer was dried.
  • the sample was developed in the developer having the following composition for 6 minutes at 20 C.
  • a photographic gelatino silver halide light-sensitive element having enhanced resistance to mechanical stress comprising:
  • R represents an alkyl group having 1 to 5 carbon atoms.
  • a photographic gelatino silver halide light-sensitive element comprising:
  • the photographic gelatino silver halide light-sensitive element of claim 6 wherein the amount of said compound is from 1 to 30% by weight based on the weight of gelatin.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US602150A 1965-12-17 1966-12-16 Gelatin-silver halide compositions containing trihydric alcohols Expired - Lifetime US3520694A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7770265 1965-12-17

Publications (1)

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US3520694A true US3520694A (en) 1970-07-14

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US (1) US3520694A (de)
BE (1) BE691333A (de)
DE (1) DE1547861C3 (de)
GB (1) GB1111930A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357419A (en) * 1981-04-02 1982-11-02 Minnesota Mining And Manufacturing Company Covering power in films
US5370986A (en) * 1990-03-05 1994-12-06 Eastman Kodak Company Stabilization of photographic recording materials

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5231737B2 (de) * 1972-11-28 1977-08-17
DE2759100A1 (de) 1977-12-30 1979-07-05 Agfa Gevaert Ag Verfahren zur haertung farbphotographischer silberhalogenidemulsionsschichten

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2960404A (en) * 1956-06-04 1960-11-15 Eastman Kodak Co Gelatin coating compositions
DE1111016B (de) * 1960-05-11 1961-07-13 Agfa Ag Verfahren zur Erzeugung photographischer Bilder nach dem Silbersalzdiffusionsverfahren

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2960404A (en) * 1956-06-04 1960-11-15 Eastman Kodak Co Gelatin coating compositions
DE1111016B (de) * 1960-05-11 1961-07-13 Agfa Ag Verfahren zur Erzeugung photographischer Bilder nach dem Silbersalzdiffusionsverfahren

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357419A (en) * 1981-04-02 1982-11-02 Minnesota Mining And Manufacturing Company Covering power in films
US5370986A (en) * 1990-03-05 1994-12-06 Eastman Kodak Company Stabilization of photographic recording materials

Also Published As

Publication number Publication date
BE691333A (de) 1967-05-29
DE1547861A1 (de) 1969-12-11
DE1547861B2 (de) 1973-04-26
GB1111930A (en) 1968-05-01
DE1547861C3 (de) 1973-11-15

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