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
  • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
  • C08G18/3275—Hydroxyamines containing two hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
  • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
  • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
  • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271

Definitions

• This invention relates to a process for improving the quality of photographic material, more particularly of silver halide emulsion layers the developability and the general light-sensitivity of which are increased.
• alkylene oxide polymers are obtained by polymerization of alkylene oxide in the presence of dehydrating products of hexitol ring compounds or aliphatic alcohols (cf. U.S. patent specifications 2,400,532 and 2,716,062) or in the presence of aliphatic acids, amines, amides or phenols (cf. U.S. patent specification 2,716,- 062).
• alkylene oxide polymers should possess a molecular weight of at least 1500 to 2000 for obtaining an appreciable increase of the sensitivity.
• condensation products are incorporated into a light-sensitive silver halide emulsion layer, their sensitivity is increased to a relatively considerable extent, the fog formation, however, in only a very small measure.
• R represents an alkyl radical, preferably a higher alkyl radical, such as a straight-chained alk-yl radical with 10 to 18 carbon atoms or a R CO radical, wherein R, has the same significance as R R represents a lower alkyleneoxyradical such as ethyleneoxy, a propyleneoxy, an isopropyleneoxy or an isobutyleneoxy radical,
• x and y each represents an integer from 1 to 50
• R represents an ethyleneoxy radical or a chain of ethyleneoxyand isopropyleneoxy radicals
• A represents a bivalent organic radical, e.g., a bivalent aliphatic, cycloaliphatic or aromatic radical or an alkylene-substituted monovalent aromatic radical, e.g.,
• condensation products are those prepared by starting from dialkanolamines and/or dialkanolamides, which contain an aliphatic hydrocarbon chain with 12 to 18 carbon atoms to which is attributed the strong surface active character of these products.
• dialkanolamides which contain an aliphatic hydrocarbon chain with 12 to 18 carbon atoms to which is attributed the strong surface active character of these products.
• coco means the alkyl radicals of the fatty acid mixture from coconut oil.
• tall- C O N wherein tall means the alkyl radicals from the fatty acid mixture from tall oil.
• diisocyanates are considered aliphatic diisocyanates, such as hexamethylene diisocyanate, as well as aromatic diisocyanates, such as toluene diisocyanate.
• polyoxyalkylene glycols are especially considered polyoxyethylene glycols.
• mixed polyoxyalkylene glycols, partlycomposed of oxyethylene units and partly of oxyisopropylene units can be used in the condensation, but the ratio of both should be chosen in such a way that finally Water-soluble products are formed.
• the average molecular weight of the polyoxyalkylene glycols used in the condensation lies preferably between 300 and 2000.
• Themolar ratio of the reaction components is preferably chosen in such a way that at least as much diisocyanate as dialkanolamine or dialkanolamide is caused to react with a sufficient amount of polyoxyalkylene glycol that water-soluble reaction products are formed.
• the condensation products of dialkanolamines or dialkanolarnides with dissocyanates are not water-soluble.
• the preferred molar ratio of the reaction components is of 2 mol of diisocyanate, 1 mol of dialkanolamine or dialkanolamide and 1 mol of polyoxyalkylene glycol.
• the condensation is carried out in an inert solvent wherein the reaction components dissolve, e.g., dioxane or benzene.
• a dialkanolamine and/ or dialkanolamide can first be precondensed at low temperature with a diisocyanate in a solvent, and then the condensation product formed can further be condensed by boiling under reflux with a polyoxyalkylene glycol.
• the reversed processing step is also possible and even more appropriate in certain cases for obtaining water-soluble products.
• condensation products are isolated in the usual way from the reaction medium by evaporation of the solvent or by precipitation into a liquid miscible with the solvent, in which liquid, however, the condensation product is not soluble.
• An appropriate precipitating means is for instance diethyl ether.
• the reaction mixture After adding the diisocyanate, the reaction mixture is further stirred for another 20 min. and a solution of 100.5 g. (0.35 mol) of lauroyldiethanolamide (melting point: 4344 C.) in 400 ccs. of anhydrous dioxone is added within 5 min. (the laurydliethanolarnide is obtained by reaction of H C-(CH -COCl with diethanolamine). By cooling with ice-water, the temperature of the reaction mixture is maintained between 20 and 25 C. After adding the amide, the reaction mixture is further stirred for another 20 min. at 20-25 C., heated to boiling point and refluxed for 4 hrs. After cooling down to room temperature again, 3.52 liters of anhydrous ether cooled to 5 C. are dropwise added. The result is a white amorphous precipitate, which is filtered off and washed with anhydrous ether. The product obtained is fully watersol-uble. Yield: 790 g. (86%).
• condensation products can be added to the coating composition of a silver halide emulsion and/or incorporated into a water-permeable layer, which applied under or over the emulsion layer forms a water-permeable system with the silver halide emulsion layer and thus can come into effective contact with the silver halide.
• the condensation products can be incorporated into the coated emulsion layer either by treating the emulsion layer with an aqueous solution of these condensation products or by coating this layer with a water-permeable layer, which contains the condensation products, or also by bringing the condensation products from a water-permeable layer lying under the emulsion layer, wherein the said condensation products are present, into effective contact with the silver halide.
• the water-soluble condensation products can be added to the light-sensitive silver halide emulsion during different preparation steps of the light-sensitive material: for instance they can be incorporated as separate addition either mixed with one or more ingredients, which are used in the preparation of the silver halide grains during the physical or chemical ripening process, or an other moment preceding the application of the emulsion.
• the development accelerators are preferably added to the silver halide emulsion composition after the chemical ripening process and just before applying the emul- SlOIl.
• condensation products are preferably added in dissolved form in water or in an aqueous mixture of water and water-miscible organic solvents that do not impair the photographic properties of the light-sensitive silver halide emulsion.
• the optimum amount of development accelerator added to the silver halide emulsion depends on the chosen compound itself, on the kind of the colloid binding agent for the silver halide grains and on the amount and the kind of the silver halide in the emulsion.
• the above-mentioned condensation products are added to the light-sensitive material in amounts from mg. to 10 g. per mol of silver halide.
• the developing bath they are normally used in amounts ranging from 0.1 g. to 10 g. per liter. If necessary, these compounds can also be added in amounts which exceed these limits.
• the step of increasing the sensitivity according to the present invention can be combined with a method known as chemical sensitization, whereby together with the mentioned condensation products usual amounts of chemical sensitizers are added to the silver halide emulsion, e.g., sulphur-containing compounds such as allyl isothiocyanate, allylthiourea or sodium thiosulphate, reducing compounds such as the tin compounds described in our Belgian patent specifications 493,464 filed January 24, 1950 and 568,687 filed June 18, 1958, the iminoaminomethanesulphinic acid compounds described in our German patent specification 1,020,868 filed March 25, 1958, or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium compounds.
• the sensitizing action of condensation products used in the present invention comes in addition to the sensitizing action of the sensitizing compounds originally present in gelatin.
• the development-accelerating compounds applied in the present invention can also be used in combination with stabilizers and fog-inhibiting compounds for the silver halide emulsion, for instance with mercury compounds or organic sulphur-containing compounds that form an insoluble silver salt with silver ions, preferably heterocyclic nitrogen-containing thione compounds such as benzothiazolin 2 thione and l-phenyltetrazolin-S- thione, the compounds described in our Belgian patent specifications 571,916 filed October 10, 1958 and 571,917 filed October 10, 8 and compounds of the oxytriazolopyrimidine type, e.g. 5-methyl-7-hydroxy-s-triazolo[1,5-a] pyrimidine. Further is also mentioned the combination with sensitizing and stabilizing cadmium salts in the lightsensitive material as well as in the developing bath.
• developmeut-accelerating compounds such as organic onium compounds and polyonium compounds, preferably of the ammonium or sul-phonium type, e.g., quaternary tetraalkylam-monium salts, alkylpyridinium salts, bis-alkylenepyridinium salts, alkylquinolinine salts and trialkylsulphonium salts can be applied together with the development accelerators used according to the invention and this in the developing solution as well as in the light-sensitive material.
• Other ingredients such as colour couplers, developing substances, hardening agents and wetting agents, can moreover be added to the emulsions in the ordinary way.
• Example 1 A washed negative gelatino-silver bromo-iodide emulsion (average grain size of the silver halide: 0.8 the silver halide of which consists of 94.5 mol percent of silver bromide and 5.5 mol percent of silver iodide is ripened at 45 C.
• the emulsion ready for coating contains per kg. 50 g. of silver halide, 75 g. of gelatin, 30 mg. of optical sensitizer with the following structural formula:
• test strip 1 This emulsion is applied to a cellulose triacetate support and dried (test strip 1).
• Other test strips are prepared by adding each time to 1 kg. of the above emulsion before coating, the amounts of development accelerators listed below. All test strips are then exposed in the same conditions through a grey wedge and developed for 7 min. at 20 C. in a bath of the following composition:
• Water c.c.s 800 Monomethyl-p-aminophenol sulfate g 2 Hydroquinone g 5 Anhydrous sodium sulfite g 100 Borax g Boric acid g 5 Potassium bromide g 0.5
• Example 2 A washed coarse-grained gelatino-silver bromo-iodide emulsion (average grain size: 1.2 composed of 98.2
• the emulsion contains per kg. g. of silver halide, 70 g. of gelatin, 50 mg. of 5-methyl-7-hydroxy-s-triaz01o-[1, 5-a]pyrimidine as stabilizer and 500 mg. saponine as wetting agent.
• test strip 1 This emulsion is applied to a cellulose triacetate support and dried (test strip 1).
• Other test strips are prepared by adding each time to 1 kg. of the above emulsion before coating 1.5 g. of the development accelerators listed below. All of the test strips are then exposed in the same conditions through a grey wedge and developed for 5 min. at 20 C. in the development composition from Exmaple 1.
• Example 3 Five identical test strips (ae) of a photographic material, prepared as in Example 1 but without development accelerators, are exposed in the same way through a grey wedge. The test strips are developed for 6 min. at 20 C.
• Test strip a is developed in a developing bath as described in Example 1.
• Each of the remaining test strips b-e is developed in a separate developing bath as described in Example 1, to which bath, however, 3 g. of the development accelerator as given in the table were added per liter.
• Example 4 A silver halide emulsion ready for coating, prepared as described in Example 1 is divided into 3 equal parts. To one of these parts no development accelerator is added (test material 1). To the remaining parts are added 1 g. of polyoxyethylene glycol, having an average molecular weight of 6000 (test material 2), and 1 g. of condensation product No. 10 (test material 3) respectively.
• the three silver halide emulsions are each applied in the same way to a separate cellulose triacetate support. After storing for 36 hrs. at 57 C. in a medium of 34% of relative humidity, the obtained test materials are exposed and developed for 10 minutes as described in Example 1.
• Process for developing photographic materials containing light-sensitive silver halide which comprises the step of developing said materials in the presence of a photographic developing agent and of a water-soluble compound formed by condensation of at least one member selected from a dialkanolamine and a dialkanolamide with an organic diisocyanate and a polyoxyalkylene glycol the amount of organic diisocyanate to said member being in the range of a molar ratio of 12:1 and the amount of said glycol being sufiicient to impart water solubility to the ultimate condensation product.
• Photographic light-sensitive element comprising a silver halide emulsion layer incorporating a water-soluble compound formed by condensation of at least one member selected from a dialkanolamine and a dialkanol-amide with an organic diisocyanate and a polyoxyalkylene glycol the amount of organic diisocyanate to said member being in the range of a molar ratio of 1-2z1 and the amount of said glycol being sufficient to impart Water solubility to the ultimate condensation product.
• Photographic developing bath comprising a silver halide photographic developing agent and in dissolved state a compound formed by condensation of at least one member selected from a dialkanolamine and a dialkanolamide with an organic diisocyanate and a polyoxyalkylene glycol the amount of organic diisocyanate to said member being in the range of a molar ratio of 12:1 and the amount of said glycol being suflicient to impart Water solubility to the ultimate condensation product.
• Photographic light-sensitive element comprising a silver halide emulsion layer incorporating a water-soluble condensation product containing recurring units of the formula:
• Photographic developing bath comprising a silver halide photographic developing agent and in dissolved state a condensation product containing recurring units of the formula:
• R is an alkyl or acyl radical
• R is a lower alkyleneoxy radical
• x and y each is an integer from 1 to 50
• R is a member selected from an ethyleneoxy radical and 10 a chain of ethyleneoxy and isopropyleneoxy radicals, and A is a bivalent organic radical.
• Photographic light-sensitive element comprising a silver halide emulsion layer incorporating a water-soluble condensation product formed by reaction of 1 mol of a member selected from dialkanolamine and dialkanolamide with 2 moles of organic diisocyanate and 1 mol of polyoxyalkylene glycol.
• Photographic developing bath comprising a silver halide photographic developing agent and in dissolved state a water-soluble condensation product formed by reaction of 1 mol of a member selected from dialkanolamine and dialkanolamide with 2 moles of organic diisocyanate and 1 mol of polyoxyalkylene glycol.
• Photographic light-sensitive element comprising a silver halide emulsion layer incorporating a water-soluble compound formed by condensation of at least one member selected from a dialkanolamine and a dialkanolamide with an organic diisocyanate and a polyoxalkylene glycol having an average molecular weight of 300 to 2000 the amount of organic diisocyanate to said member being in the range of a molar ratio of l2:1 and the amount of said glycol being sufficient to impart water solubility to the ultimate condensation product.
• Photographic developing bath comprising a silver halide photographic developing agent and in dissolved state a Water-soluble compound formed by condensation of at least one member selected from a dialkanolamine and a dialkanolamide with an organic diisocyanate and a polyoxyalkylene glycol having an average molecular weight of 300 to 2000 the amount of organic diisocyanate to said member being in the range of a molar ratio of l2:1 and the amount of said glycol being sufficient to impart water solubility to the ultimate condensation product.
• Photographic light-sensitive element comprising a silver halide emulsion layer incorporating per mol of silver halide mg. to 10 g. of water-soluble compound formed by condensation of at least one member selected from a dialkanolamine and a dialkanolamide with an organic diisocyanate and a polyoxyalkylene glycol the amount of organic diisocyanate to said member being in the range of a molar ratio of l-2z1 and the amount of said glycol being suflicient to impart water solubility to the ultimate condensation product.
• Photographic developing bath comprising a silver halide photographic developing agent and in dissolved state and per liter 0.1 g. to 10 g. of a compound formed by condensation of at least one member selected from a dialkanolamine and a dialkanolamide with an organic diisocyanate and a polyoxyalkylene glycol the amount of organic diisocyanate to said member being in the range of a molar ratio of 12:1 and the amount of said glycol being suificient to impart water solubility to the ultimate condensation product.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
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• Silver Salt Photography Or Processing Solution Therefor (AREA)
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Cited By (14)

• 1964
  • 1964-06-02 BE BE43694A patent/BE648710A/xx unknown
  • 1964-10-01 DE DE1447698A patent/DE1447698C3/de not_active Expired
• 1965
  • 1965-05-20 GB GB21375/65A patent/GB1091705A/en not_active Expired
  • 1965-05-24 US US458489A patent/US3307948A/en not_active Expired - Lifetime

Non-Patent Citations (1)

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