US3321312A - Stabilized polyalkylene oxide sensitized emulsions - Google Patents

Stabilized polyalkylene oxide sensitized emulsions Download PDF

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Publication number
US3321312A
US3321312A US331937A US33193763A US3321312A US 3321312 A US3321312 A US 3321312A US 331937 A US331937 A US 331937A US 33193763 A US33193763 A US 33193763A US 3321312 A US3321312 A US 3321312A
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US
United States
Prior art keywords
emulsion
compounds
silver halide
polyalkylene oxide
emulsions
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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US331937A
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English (en)
Inventor
Muller-Bardorff Wolfgang
Saleck Wilhelm
Ulrich Hans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
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Agfa AG
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Publication date
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Publication of US3321312A publication Critical patent/US3321312A/en
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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
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
    • 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 invention relates to the stabilization of photographic materials which contain at least one silver halide emulsion layer sensitized with an alkylene oxide polymerization product, using a stabilizer combination of a known stabilizer and ortho-hydroxybenzylidene or orthohydroxy benzylamine derivatives.
  • alkylene oxide derivatives for example, ethylene oxide polymerisation products.
  • the alkylene oxide derivatives are, however, of limited utility since they produce a considerable fogging and since they impair the keeping properties of the emulsion.
  • stbilizer additives have the disadvantage that although they partly reduce the fogging and partly reduce the loss in sensitivity of the photographic materials sensitized wit-h polyalkylene oxide derivatives during storage, they never quite eliminate both these defects, even if they are applied in combination with each other.
  • Other objects of the invention will become apparent from a consideration of the following description and examples.
  • X represents an alkylene group with preferably up to carbon atoms or an arylene group preferably phenylene; R stands for a sulfo group, carboxylic group an OSO H group or salts thereof.
  • R stands for a sulfo group, carboxylic group an OSO H group or salts thereof.
  • the benzene ring 3,321,312 Patented May 23, 1967 of the general formulae as well as the substituent X may in turn be substituted.
  • Halogen in particular chlorine, hydroxyl, lower alkyl, preferably up to 5 carbon atoms, lower alkoxy, preferably up to 5 carbon atoms, sulfo or carboxyl.
  • the compounds of the above general formulae not only prevent the fogging and the loss of sensitivity upon storage of the silver halide emulsions, but also produce a further increase in sensitivity.
  • Suitable compounds are, for example:
  • the azomethine compounds may 'be prepared by reacting, in aqueous solution, one mol of an alkali metal salt of an amino acid with one mol of an :aldehyde which may be substituted. The hydrogenation of the azomethine compounds is easily performed in aqueous solution with the aid of a Raney nickel catalyst.
  • the compounds of the present invention can be added to all photographic silver halide emulsions, the silver halide of which may consist of silver chloride, bromide, iodide or mixtures thereof, although silver iodo bromide emulsions are preferred.
  • hydrophilic colloidal materials such as proteins, in particular gelatine, synthetic resins for instance, polyvinyl compounds, such as polyvinyl alcohol, polyvinyl pyrrolidone, or the like.
  • the emulsions can be further chemically sensitized by any of the known compounds and procedures, for example, the emulsions can be treated with labile sulfur compounds, such as sodium sulfite, thiourea, thiocyanates, alkali salts of thiocyanates, or salts of the noble metals, such as ruthenium, rhodium, palladium, iridium, and platinum.
  • labile sulfur compounds such as sodium sulfite, thiourea, thiocyanates, alkali salts of thiocyanates, or salts of the noble metals, such as ruthenium, rhodium, palladium, iridium, and platinum.
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite.
  • the emulsions can also be chemically sensitized with gold salts such as potassium chloroaurite, potassium aurithiocyanate potassium ohloroaurate, auric trichloride and 2-aurosulfobenzthiazole methochloride.
  • gold salts such as potassium chloroaurite, potassium aurithiocyanate potassium ohloroaurate, auric trichloride and 2-aurosulfobenzthiazole methochloride.
  • the emulsions can also be optically sensitized with, for example, cyanine or merocyanines.
  • photographic stabilizers are suitable as basic stabilizer in combination with the compounds according to the invention.
  • suitable are:
  • the basic stabilizers are added in an amount of 5 to 2000 mg. per liter of the emulsion.
  • polyalkylene oxides there may be used the condensation products of alkylene oxides preferably ethylene oxide, with each other or with aliphatic alcohols, acids and amines or phenols.
  • alkylene oxides preferably ethylene oxide
  • Polyethylene oxides which contain quaternary nitrogen groups are also suitable. It is preferred to use products which have a molecular weight of at least 1500 preferably of between 1500 and 3000.
  • the quantity to be used depends on the silver halide content of the emulsion and varies between 0.01 g. and 1 g. per 1 kg. of emulsion. The optimum quantity must be 'determined for each emulsion.
  • the ortho-h-ydroxybenzylor benzylideneamino compounds according to the invention are preferably added to the emulsion before chemical ripening or after-ripening.
  • the solubility of the compounds of the invention is dependent upon the substituents, some are soluble in organic solvents, others in Water or aqueous solutions of acids or alkalis, such as alkali metal hydroxides, carbonates, phosphates or the like.
  • the compounds are used in concentration of 0.01 g. to 1 g. per 1 kg. emulsion (preferably 0.35 g./kg.).
  • concentration 0.01 g. to 1 g. per 1 kg. emulsion (preferably 0.35 g./kg.).
  • the optimum quantity to be added depends on the compound and on the type of emulsion. It may easily be determined by a. few tests.
  • the compounds may also be incorporated in the finished photographic layer in a bath.
  • the stabilizers according to the invention can also be used for color photographic materials.
  • the color couplers can be incorporated into the emulsion layer in a dissolved diffusion-resistant form. According to another method the color coupler is first dissolved in an oily organic material and this combination is then dispersed in a finely divided state throughout the emulsion.
  • the developer according to the invention can also be used in those processes in which the so-called Successive Colorant Formation is applied. In this process the color coupler is incorporated into the colorforming developer composition.
  • the successive color formation in each of the single layers of a multilayer material is obtained by controlled penetration of the processing solution. For example, in an integral tripack it is possible by means of a loaded dye coupling developer to develop the top layer of the material without affecting the lower emulsion layers if the time of development is carefully controlled.
  • Example 1 A very highly sensitive silver bromide iodide gelatine emulsion containing 4 mol. percent of iodide is prepared according to common practice.
  • the emulsion contains silverhalide in an amount corresponding to 50 grams of silver per liter.
  • the chemical ripening or after-ripening is performed in the usual manner.
  • As ripening additives are used 35 to 40 mg. of KBr per liter of emulsion and a gold thiocyanate solution. This emulsion is divided into 3 parts, A, B and C.
  • Part A is used for comparison without further additives.
  • Part B is treated with 300 mg./l. of compound 1.
  • Part C is treated with 600 mg./l. of compound 1.
  • All three samples A, B and C are after-ripened until the maximum sensitivity is obtained. Thereafter, they are sensitized panchromatically adding one or more suitable sensitizing dyes. In this state of the production are further added a stabilizer in an amount of 200 mg. per liter, for example, an azaindolizine, particularly 7-hydroxy-5- methyl-triazaindolizin and 200 mg. per liter of a polyethylene oxide, having a molecular weight of about 2000.
  • the final emulsion is applied to a conventional support, such as a film of cellulose acetate, polycarbonate on the basis of bis-hydroxy-phenyl alkanes, polyesters, in particular of terephthalic acid and ethylen glycol, and the like.
  • an increase in sensitivity of 3 corresponds to an increase by one light stop.
  • Example 2 A very highly sensitive silver iodo bromide emulsion as described in Example 1 is divided into three parts, A, B, and C.
  • Part A is tested without further additives for comparison.
  • Part B is treated with 300 mg./l. of compound IV.
  • Part C is treated with 600 mg./l. of compound IV.
  • Example 1 The three samples A, B and C are now treated as indicated in Example 1, the photographic material thus produced is stored for five months, a portion of the material is exposed for three days to a temperature of 60 in a heating cupboard and this material is then exposed and developed and compared with the corresponding samples which have been stored at normal temperature.
  • Example 3 A very highly sensitive silver iodo bromide emulsion described in Example 1 is divided into three parts, A, B and C.
  • Part A is ripened without further additives to be used for comparison.
  • Part B is treated with 300 mg./l. of compound VIII.
  • Part C is treated with 600 mg./l. of compound VIII.
  • Example 1 All three samples A, B and C are then treated as indicated in Example 1, the photographic material thus produced is stored for five months and a portion of the material is subjected for three days to a temperature of 60 in a heating cupboard. The material is then exposed and developed as also, for comparison, the corresponding samples which have been stored at normal temperature.
  • the compounds of the present invention can be used in their acid form.
  • the compounds can further be applied as salts of alkali metals, in particular sodium or potassium, or salts of ammonia or organic amides.
  • a photographic silver halide emulsion wherein the vehicle for the silver halide is a water-permeable hydro philic colloid and wherein said emulsion contains (1) an effective amount of a basic stabilizer;
  • X is a divalent radical of the group consisting of alkylene, having up to 5 carbon atoms and arylene and wherein R represents an acid radical of the group consisting of sulfo carboxylic -OSO H and a salt of the said acid radicals and both the 7 benzene ring and X can be substituted by halogen, hydroxyl, lower alkyl, lower alkoxy, sulfo or carboxyl.

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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)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
US331937A 1963-01-05 1963-12-19 Stabilized polyalkylene oxide sensitized emulsions Expired - Lifetime US3321312A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA42031A DE1170777B (de) 1963-01-05 1963-01-05 Stabilisiertes photographisches Material

Publications (1)

Publication Number Publication Date
US3321312A true US3321312A (en) 1967-05-23

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Country Status (5)

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US (1) US3321312A (en)van)
BE (1) BE642085A (en)van)
CH (1) CH449415A (en)van)
DE (1) DE1170777B (en)van)
GB (1) GB1038345A (en)van)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3434842A (en) * 1964-08-08 1969-03-25 Agfa Gevaert Ag Photographic silver halide emulsions stabilized with 2-imino-thiazolones
US3915713A (en) * 1972-11-02 1975-10-28 Fuji Photo Film Co Ltd Silver halide photographic emulsion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3434842A (en) * 1964-08-08 1969-03-25 Agfa Gevaert Ag Photographic silver halide emulsions stabilized with 2-imino-thiazolones
US3915713A (en) * 1972-11-02 1975-10-28 Fuji Photo Film Co Ltd Silver halide photographic emulsion

Also Published As

Publication number Publication date
BE642085A (en)van) 1964-07-03
DE1170777B (de) 1964-05-21
GB1038345A (en) 1966-08-10
CH449415A (de) 1967-12-31

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