US3813250A - Silver halide photosensitive element containing an antifogging combination of a nitrated heterocyclic compound and a polymeric stabilizer - Google Patents

Silver halide photosensitive element containing an antifogging combination of a nitrated heterocyclic compound and a polymeric stabilizer Download PDF

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Publication number
US3813250A
US3813250A US00296492A US29649272A US3813250A US 3813250 A US3813250 A US 3813250A US 00296492 A US00296492 A US 00296492A US 29649272 A US29649272 A US 29649272A US 3813250 A US3813250 A US 3813250A
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United States
Prior art keywords
silver halide
carbon atoms
general formula
vinyl
alkyl group
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Expired - Lifetime
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US00296492A
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English (en)
Inventor
Y Takamura
T Miyazako
Y Nakajima
R Ohi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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 polymers within the scope of the general formula (II) include homopolymers composed of the recurring unit represented by the formula (II); copolymers composed of two or more difierent recurring units represented by the formula (II); and copolymers composed of greater than 50 mol percent of at least one recurring unit represented by the formula (II) and at least one monomer which is copolymerizable with the above recurring unit.
  • Examples of the monomer which is copolymerizable with the recurring unit of the formula (II) include the recurring unit represented by general formula (III) wherein R represents a hydrogen atom or a methyl group, and Z represents OR wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; OCOR wherein R is an alkyl group having 1 to 4 carbon atoms; OOOR wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy or an alkyl group having 1 to 4 carbon atoms;
  • recurring units which are copolymerizable with the above recurring unit of the formula (II) include maleic anhydride, maleic acid, a half-ester of maleic acid, a half-amide of maleic acid and the like.
  • the preferred polymers are those containing vinylpyrrolidone as the recurring unit of the formula (II).
  • Homopolymers having recurring units represented by general formula II are exemplified by the following compounds.
  • Compound I preferably is incorporated in an amount of from about 0.5 to about 250 mg., more desirably from 0.5 to mg., per mole of silver halide contained in a silver halide emulsion, and compound II is incorporated in an amount of from about 0.05 to about 15 g., preferably from 0.05 to g., per mole of silver halide.
  • aforesaid compounds I and H in an emulsion during the period from the second ageing to just before application of the emulsion to a support.
  • a portion or the total amount of the compounds may be incorporated in a layer adjacent the emulsion layer.
  • the total amounts of each of the compounds I and II in both layers can be the same amounts as those described for the com pounds I and II contained in only the emulsion layer, i.e., the total amounts of each of the compounds I and II in the emulsion layer and a layer adjacent to the emulsion layer can range from about 0.5 to about 250 mg., preferably from 0.5 to 100 mg., per mole of silver halide contained in the silver halide emulsion layer and from about 0.05 to about 15 g., preferably from 0.05 to 5 g., per mole of the silver halide contained in the silver halide emulsion layer, respectively.
  • the present invention is applicable to any silver halide emulsion, such as silver iodide emulsions, silver chlorobromide emulsions and silver chloroiodobromide emulsions.
  • the emulsions may be sulfur-sensitized, gold-sensitized or reductively sensitized or may have incorporated therein spectral sensitizers, polyalkylene oxide-type sensitizers, various stabilizers, hardeners, coating assistants, couplers or like conventional adjuvants.
  • Any conventional support for photosensitive materials may be used in accordance with the present invention, e.g., glass, cellulose acetate films, poly(ethylene terephthalate) films, polycarbonate films, polystyrene films, polypropylene film, baryta paper and like conventional sheet materials which have been used as supports for silver halide photo-emulsions.
  • the fog in the silver halide photosensitive materials is minimized with a minimum decrease in sensitivity.
  • EXAMPLE 1 A high sensitivity X-ray gelatin-silver iodobromide emulsion containing 1.5 mol percent of silver iodide (based on silver bromide) which was sulfur-sensitized by sodium thiosulfate and gold-sensitized by gold chloride containing 4-hydroxy-6-methyl-l,3,3a,7-tetrazoindene in an amount of 0.5 g./mol AgX, saponin in an amount of 0.5 g./mol AgX and mucochloric acid in an amount of 0.15 g./mol AgX was divided into 23 portions.
  • Relative sensitivity stands for a relative value of sensitivity at the density of fog +0.3 referring to as the control value.
  • EXAMPLE 2 The same high sensitivity X-ray gelatin-silver iodobromide emulsion as was used in Example 1 was, after the addition of a stabilizer, a wetting agent and a hardener as in Example 1, divided into 5 portions, Compound II-7 was added to certain portions, or not added, in the amounts as indicated in Table 2.
  • Table 2 shows that it is possible to obtain a result similar to Example 1 by incorporating one component of the anti-fogging agent of the present invention into an emulsion layer and the other into an adjacent layer.
  • Table 1 shows that the addition of compound I alone EXAMPLE 3
  • Table 3 shows that the anti-fogging agent of the present invention reduces fog with only a slight decrease in sensitivity in color photographic emulsions.
  • EXAMPLE 4 The same high sensitivity X-ray gelatin-silver iodobromide emulsion as was used in Example 1 had added thereto a stabilizer, a wetting agent and a hardener as in Example 1, and was divided into 5 portions. To each portion was added an anti-fogging compound, as listed in Table 4, and the portions then applied to a poly(ethylene terephthalate) base and dried to provide specimens. The specimens were exposed and developed under the same conditions as in Example 1 and subjected to relative sensitivity and fog determinations. The results thus obtained are summerized in Table 4. As indicated by Table 4, there were obtained silver halide photosensitive materials with a high relative sensitivity and a reduced fog, as in Example 1.
  • III-1 0.15 (corresponding to a molecular weight of 10,000).
  • III-1: 11] 0.28 (corresponding to a molecular weight of 30,000) a 7:3 copolymer of N-vinylpyrrolidone with vinyl alcohol.
  • N/ t m where X and Y individually represent N or CR wherein R represents a hydrogen atom or alkyl group containing 1 to 4 carbon atoms; and (b) at least one member selected from polymers containing greater than 50 mol percent of the recurring unit represented by the general formula i l.
  • R and R individually represent a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms or form, when taken together with the nitrogen and carbon atoms to which they are attached, a 5- to 7-membered heterocyclic ring selected from the group consisting of pyrrolidone, piperidone and caprolactam, said polymers being homopolymers composed of the recurring unit represented by the formula (II); copolymers composed of two or more different recurring units represented by the formula (II); and copolymers composed of greater than 50 mol percent of at least one recurring unit represented by the formula (II) and at least one monomer which is copolymerizable with the above recurring unit, said monomer having the general formula (III) Z (III) wherein R represents a hydrogen atom or methyl group, and Z represents -OR wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; OCOR wherein R is a hydrogen atom or an alkyl group having 1 to 4
  • R1 CON wherein R and R each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with hydroxy or an alkyl group having 1 to 4 carbon atoms, or form, when taken together with the nitrogen atom to which they are attached,
  • R represents an alkylene chain having 2 to 3 carbon atoms and R and R each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; CN; phenyl or sulfophenyl; or a pyridyl ring, the compound of general formula (I) being contained in an amount of from about 0.5 to about 250 mg. per mole of silver halide and the polymer containing greater than 50 mole percent of the recurring unit represented by the general formula (II) being contained in an amount from about 0.05 to about 15 g. per mole of silver halide.
  • the silver halide photosensitive material as in claim 1 which further comprises a layer adjacent to said silver halide emulsion layer.
  • the silver halide photosensitive material as in claim 1 in which the copolymer having recurring units represented by general formula II is present and is contained in an amount of about 0.05 to about 15 g. per mol of silver halide.
  • the silver halide photosensitive material as in claim 1 which contains a compound represented by general formula I and a homopolymer having recurring units represented by general formula II.
  • the silver halide photosensitive material as in claim 1 which contains a compound represented by general formula I and a copolymer having recurring units represented by general formula II.
  • the silver halide photosensitive material as in claim 1 in which the homopolymer having recurring units represented by general formula II is present and is contained in an amount of about 0.05 to about 15 g. per mol of silver halide.
  • the compound represented bygeneral formula (I) is selected from the group consisting of S-nitrobenztriazole, S-nitroindazole, fi-nitroindazole, -nitrobenzimidazole nitrate, 4-nitrobenzimidazole and 2-ethyl- S-nitrobenzimidazole.
  • the silver halide photosensitive material as in claim 1 wherein said polymer containing greater than 50 mole percent of the recurring unit represented by the general formula (II) is a homopolymer selected from the group consisting of poly-N-vinyl-N-methylformamide, poly-N- vinyl-N-methylacetamide, poly-N-vinyl-N-methylpropionamide, poly-N-vinyl-N-ethylformamide, poIy-N-vinyl-N- ethylacetamide, poly-N-vinyl-N-ethylpropionamide, poly- N-vinylpyrrolidone, poly-N-vinylpiperidone and poly-N- vinylcaprolactam.
  • the silver halide photosensitive material as in claim 1 in which any homopolymer or copolymer has a molecular weight of from about 4,000 to about 1,000,000.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US00296492A 1971-10-11 1972-10-10 Silver halide photosensitive element containing an antifogging combination of a nitrated heterocyclic compound and a polymeric stabilizer Expired - Lifetime US3813250A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP46079979A JPS515937B2 (is") 1971-10-11 1971-10-11

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US3813250A true US3813250A (en) 1974-05-28

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US00296492A Expired - Lifetime US3813250A (en) 1971-10-11 1972-10-10 Silver halide photosensitive element containing an antifogging combination of a nitrated heterocyclic compound and a polymeric stabilizer

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US (1) US3813250A (is")
JP (1) JPS515937B2 (is")
CA (1) CA1006739A (is")
DE (1) DE2249889C2 (is")
FR (1) FR2156199B1 (is")
GB (1) GB1353259A (is")

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4469784A (en) * 1981-09-28 1984-09-04 Fuji Photo Film Co., Ltd. Silver halide emulsions
US4528264A (en) * 1982-11-16 1985-07-09 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US5272045A (en) * 1992-11-13 1993-12-21 Sun Chemical Corporation Water soluble antifoggant for powder developer solutions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE619938A (is") * 1961-07-10
BE625436A (is") * 1961-11-29
US3518086A (en) * 1967-04-18 1970-06-30 Gaf Corp Silver halide emulsions for lithography

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4469784A (en) * 1981-09-28 1984-09-04 Fuji Photo Film Co., Ltd. Silver halide emulsions
US4528264A (en) * 1982-11-16 1985-07-09 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US5272045A (en) * 1992-11-13 1993-12-21 Sun Chemical Corporation Water soluble antifoggant for powder developer solutions

Also Published As

Publication number Publication date
JPS515937B2 (is") 1976-02-24
FR2156199B1 (is") 1977-08-26
DE2249889A1 (de) 1973-04-19
FR2156199A1 (is") 1973-05-25
GB1353259A (en) 1974-05-15
DE2249889C2 (de) 1986-01-30
CA1006739A (en) 1977-03-15
JPS4845230A (is") 1973-06-28

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