US3408199A - Photographic material with improved silver covering power - Google Patents

Photographic material with improved silver covering power Download PDF

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Publication number
US3408199A
US3408199A US465769A US46576965A US3408199A US 3408199 A US3408199 A US 3408199A US 465769 A US465769 A US 465769A US 46576965 A US46576965 A US 46576965A US 3408199 A US3408199 A US 3408199A
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US
United States
Prior art keywords
covering power
silver
silver halide
carbon atoms
photographic
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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US465769A
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English (en)
Inventor
Saleck Wilhelm
Dinges Karl
Muller Erwin
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C1/04—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine

Definitions

  • the invention relates to photographic material with at least one silver halide emulsion layer having improved photographic characteristics. More particular the invention relates to a method for increasing the covering power of developed silver and improving the maximum density, contrast and speed of gelatino silver halide emulsions.
  • the object of the present invention is to provide substances which increase the silver covering power of silver halide layers without, at the same time, producing any deterioration in the photographic properties.
  • Another object is to provide photographic silver halide emulsions demonstrating increased covering power of the developed silver.
  • silver halide gelatin emulsions of increased covering power of the developed silver and enhanced properties can be made by adding to the emulsions an effective amount of polymers or copolymers of derivatives of N-methylol methacrylamide or of N- methylol acrylamide.
  • X represents the groups 7 h V -CH2O-Rz o CH2-0i J-Rz R represents an alkyl radical preferably containing up to 3 carbon atoms and R represents a methyl group or hydrogen.
  • the polymeric products to be employed in accordance with the invention preferably have a molecular weight up to 100,000.
  • the molecular weight is not critical. The most suitable molecular weight range may be determined by simple comparison tests.
  • the silver covering power is very considerably increased by the polymers according to the invention, so that, even when added in relatively small quantities, they produce marked eflects.
  • they exhibit the surprising property of eliminating fogging and, to some extent, of increasing sensitivity. In this respect it is particularly remarkable that the fog-inhibiting effect even occurs under extreme conditions, for example on prolonged storage in a heating chamber at 60.
  • the polymers to be used in the manner according to the invention may be prepared by known processes. Useful methods are described, for example, in Die makromolekulare Chemie, vol. 57 (1962), pages 27-51.
  • Polymerization is finished after 5 to 6 hours at 70 C., the polymer precipitating as a white powder. After cooling, 100 g. of acetone are added and the mixture is suction-filtered.
  • Copolymers of methacrylamide N methylol methylether Copolymeri'sation is performed in analogous manner except that the benzene is replaced by a mixture of 415 g. of benzene and 415 g. of ethylacetate.
  • the polymers according to the invention may be added to the light-sensitive silver halide emulsion layers or to any auxiliary layers such as intermediate or protective layers. They may be added at any stage in the preparation of the emulsion or to the casting solutions for the layers. They are used in the form of aqueous solutions containing 10 to by weight of the polymer.
  • the colorless polymer powders are generally soluble in warm water at a temperature of 30 to 50 C.
  • the polymers according to the invention are added to the layers in quantities varying from 5 g. to 140 g., preferably from 10 g. to 50 g. per mol of silver halide.
  • concentrations in which they are used depend upon the desired effect, the silver content of the emulsion and the type of silver halide used. The most favourable concentration may be determined in known manner by some comparison tests.
  • the photographic emulsions in which the compounds according to the invention are used may be chemically sensitized in the usual way, for example, by polyethylene oxides, quaternary ammonium compounds or sulfur compounds, as described, for example, in the book by Mees entitled The theory of the Photographic Process (1954), pages 149 to 169.
  • the emulsions may be further chemically sensitized by the addition of noble metal compounds, such as gold, rhodium, palladium, ruthenium, iridium and platinum compounds.
  • the emulsions may also be sensitized by reducing agents, for example, stannous salts or polyamides.
  • optically sensitized emulsions which contain the conventional cyanine, merocyanine or rhodacyanine sensitizing dyes.
  • Dyes which may be used are described in F. M. Hamers book The Cyanine Dyes and Related Compounds, Interscience Publishers, 1964.
  • the emulsions may be stabilized with known compounds such as mercury compounds, triazoles, for example, mercapto-phenyltriazoles, or azaindenes which are described, for example, in the article by Birr in the Journal Wiss. Photographic vol. 47 (1952), pages 2 to 28.
  • known compounds such as mercury compounds, triazoles, for example, mercapto-phenyltriazoles, or azaindenes which are described, for example, in the article by Birr in the Journal Wiss. Photographic vol. 47 (1952), pages 2 to 28.
  • the binding agent used for the layers is preferably gelatin which may be completely or partly replaced by other water-permeable film-forming colloids, such as alginic acid and its derivatives, for example, alkalimetal salts or esters preferably with lower aliphatic alcohols, polyvinyl pyrrolidones, starch or carboxyalkyl cellulose such as carboxymethylcellulose.
  • alginic acid and its derivatives for example, alkalimetal salts or esters preferably with lower aliphatic alcohols, polyvinyl pyrrolidones, starch or carboxyalkyl cellulose such as carboxymethylcellulose.
  • EXAMPLE 1 a hardening agent, for example, one of the hardening agents described in German Patent Specification No. 872,153, and is then divided up into a number of samples. One sample is used for comparison, whilst 50 ml. and ml. per liter, respectively, of a 20% by Weight aqueous solution of polymethacrylamide N methylolmethyl ether are added to second and third samples.
  • a hardening agent for example, one of the hardening agents described in German Patent Specification No. 872,153
  • the last two samples contain less silver halide per m9 of the light-sensitive layer.
  • the three samples After exposure in a sensitometer behind a grey /2 step wedge, the three samples are developed for five minutes at 20 C. in a developer of the following composition:
  • EXAMPLE 3 50 ml. of a 20% by weight solution of polymethacrylamide-N-methylohnethylether is added to a silver halide emulsion of the type used in Example 1, after which the emulsion is poured onto a support of polyethylenglycol terephthalate as described above.
  • the light-sensitive emulsion layer is coated with a protective layer containing as sensitizer a polyethylene oxide having a molecular weight of 4500 (Sample G).
  • a mercury stabilizer 0.4 mg./l. of mercury thiazole chloride
  • Example H a mercury stabilizer
  • EXAMPLE 4 To a silver halide emulsion as described in Example 1, are added 50 ml. of a 20% by weight solution of a copolymer of 75% by weight of N-methylmethacrylamide and 25% by weight of acrylic acid, according to Belgian Patent specification No. 620,515. The material is processed as described in the previous examples.
  • a light-sensitive material comprising at least one light sensitive silver halide emulsion layer having improved covering power of developed silver which contains a polymeric product with at least 15 mol percent of units of the following formula:
  • R represents a member of the group consiiting of hydrogen and methyl and R stands for an alkyl radical containing up to 3 carbon atoms.
  • a light-sensitive material comprising at least one light-sensitive silver halide emulsion layer having im proved covering power of developed silver which contains a polymeric product consisting of a homopolymer of a monomer of the group consisting of an ester of N-methylolacrylamide the ester grouping of which has up to 4 carbon atoms, an ether of N-methylolacrylamide the ether grouping of which has up to 3 carbon atoms, an ester of N-methylol methacrylamide the ester grouping of which has up to 4 carbon atoms and an ether of N-methylol methacrylamide the ether grouping of which has up to 3 carbon atoms.
  • a light-sensitive material comprising at least one light-sensitive silver halide emulsion layer having improved covering power of developed silver, which contains a polymeric product with at least 15 mol percent of units of the group consisting of ethers of N-methylol acrylamide, the ether grouping of which has up to 3 carbon atoms, esters of N-methylol acrylamide, the ester grouping of which has up to 4 carbon atcms, ethers of N-methylol methacrylamide, the ether grouping of which has up to 3 carbon atoms or esters of N-methylol methacrylamide, the ester grouping of which has up to 4 carbon atoms and up to mol percent of polymerized units of a monomer of the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-alkylacrylamide, Naalkylrnethacrylamide, acrylic acid esters the ester grouping of which has up to 5 carbon atoms, methacrylic esters the este

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US465769A 1964-07-04 1965-06-21 Photographic material with improved silver covering power Expired - Lifetime US3408199A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA0046506 1964-07-04

Publications (1)

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US3408199A true US3408199A (en) 1968-10-29

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US (1) US3408199A (enrdf_load_stackoverflow)
BE (1) BE666067A (enrdf_load_stackoverflow)
CH (1) CH454614A (enrdf_load_stackoverflow)
GB (1) GB1069944A (enrdf_load_stackoverflow)
NL (1) NL6508535A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3713829A (en) * 1965-06-01 1973-01-30 Fuji Photo Film Co Ltd Photographic light sensitive material containing copolymer layer
US3957492A (en) * 1973-01-08 1976-05-18 Fuji Photo Film Co., Ltd. Photographic silver halide emulsion comprising an amphoteric copolymer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE790872A (nl) * 1971-11-08 1973-05-03 Agfa Gevaert Nv Ontwikkelbehandeling van fotografische zilverhalogenidematerialen bij hoge temperaturen

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2533166A (en) * 1945-10-16 1950-12-05 Gen Aniline & Film Corp Process for polymerizing watersoluble polyacrylamides and poly-alpha-substituted acrylamides
US2593888A (en) * 1945-10-16 1952-04-22 Gen Aniline & Film Corp Production of hydroxyalkyl amides of acrylic acids
US3069263A (en) * 1958-12-17 1962-12-18 Polaroid Corp Photographic products and processes using alkali permeable polymeric layers
US3178295A (en) * 1961-07-27 1965-04-13 Eastman Kodak Co Photographic silver halide emulsions fog stabilized with copolymers of n, n-di-normal-butylacrylamide and acrylic acid
US3178296A (en) * 1961-07-27 1965-04-13 Eastman Kodak Co Photographic gelatino-silver halide emulsions containing polymeric addenda to increase covering power
US3341332A (en) * 1963-07-24 1967-09-12 Fuji Photo Film Co Ltd Light-sensitive photographic material containing polyalkenoylmorpholine

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2533166A (en) * 1945-10-16 1950-12-05 Gen Aniline & Film Corp Process for polymerizing watersoluble polyacrylamides and poly-alpha-substituted acrylamides
US2593888A (en) * 1945-10-16 1952-04-22 Gen Aniline & Film Corp Production of hydroxyalkyl amides of acrylic acids
US3069263A (en) * 1958-12-17 1962-12-18 Polaroid Corp Photographic products and processes using alkali permeable polymeric layers
US3178295A (en) * 1961-07-27 1965-04-13 Eastman Kodak Co Photographic silver halide emulsions fog stabilized with copolymers of n, n-di-normal-butylacrylamide and acrylic acid
US3178296A (en) * 1961-07-27 1965-04-13 Eastman Kodak Co Photographic gelatino-silver halide emulsions containing polymeric addenda to increase covering power
US3341332A (en) * 1963-07-24 1967-09-12 Fuji Photo Film Co Ltd Light-sensitive photographic material containing polyalkenoylmorpholine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3713829A (en) * 1965-06-01 1973-01-30 Fuji Photo Film Co Ltd Photographic light sensitive material containing copolymer layer
US3957492A (en) * 1973-01-08 1976-05-18 Fuji Photo Film Co., Ltd. Photographic silver halide emulsion comprising an amphoteric copolymer

Also Published As

Publication number Publication date
DE1447582B2 (de) 1975-11-27
DE1447582A1 (de) 1969-05-29
CH454614A (de) 1968-04-15
BE666067A (enrdf_load_stackoverflow) 1965-12-29
NL6508535A (enrdf_load_stackoverflow) 1965-12-27
GB1069944A (en) 1967-05-24

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