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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols

Definitions

• Z being a straight-chain or branched-chain C -C alkylene group.
• the speed and developability of the silver halide element is substantially increased by the presence of this polyaddition compound.
• infectious development of silver chloride and silver chlorobromide emulsions it is possible by means of these polyaddition compounds to obtain very contrasty line and screen images and sharply defined screen dots and to reduce the formation of peppers when using somewhat exhausted developing baths.
• This invention relates to a process for producing photographic silver images by development of an exposed lightsensitive silver halide in the presence of compounds influencing the sensitometric characteristics of light-sensitive silver halide emulsions by an increase of the speed and/or the gradation.
• the present invention further relates to the compounds used in said process, to their preparation and to photographic materials and developing baths containing said compounds.
• Polyoxyalkylene compounds when used in silver halide emulsion layers, impair the keeping qualities of these layers, particularly at high temperatures and elevated degrees of relative humidities in that they induce a substantial increase of fog. It was also found that when these polyoxyalkylene compounds are incorporated into silver halide emulsions to increase the speed, they very often impair the image tone of the developed silver by forming brown and reddish brown images. Moreover, polyoxyalkylene compounds when used in infectious development greatly increase the formation of peppers.
• Peppers are black spots of a very high density which are irregularly produced during the development in the areas of the light-sensitive emulsion which are slightly exposed. These peppers when they are present in a high amount markedly degrade the quality of a screen image reproduction by deforming the screen dots and/or soiling the areas which were practically unexposed. The phenomenon of pepper particularly arises when partly air oxidized or somewhat exhausted developing baths are used.
• the invention further provides photographic lightsensitive silver halide materials and photographic developing compositions comprising a water-soluble polymeric compound obtained by polyaddition of a dihydric alcohol and a bisepoxide as defined hereinafter.
• the water-soluble polymeric compounds of use according to the present invention are obtained by polyaddition of a dihydric alcohol corresponding to the formula:
• Z stands for a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms and may contain one or more oxygen bridges, for example, ethylene, tetramethylene, l-methyltrimethylene, and ethyleneoxy-ethylene.
• the water-soluble polymeric compounds for use in accordance with the present invention are compounds comprising units of the following structure:
• the compounds of use according to the present invention are prepared by reaction of a dihydric alcohol with a bisepoxide as defined above.
• the starting products are made to react in an equimolar ratio, though an excess of one of them is not harmful since the reaction proceeds very smoothly and generally not in an exothermic way.
• the following general procedure can be given for the preparation of the polyaddition compounds of use according to the present invention.
• the possible epoxide groups in the final product obtained which may be due to unreacted bisepoxide or which are terminal epoxide groups in the polyaddition compounds formed, are determined by titration with perchloric acid in acetic acid medium comprising hexadecyl trimethyl ammonium bromide.
• the residual epoxide groups are given on a percentage basis of the milliequivalents of epoxide groups found relative to the milliequivalents of epoxide groups used on starting the reaction.
• the hydrogen atoms of the free hydroxyl groups in the polyaddition compounds obtained may be partly or wholly substituted by reaction with compounds which are reactive with respect to an active hydrogen atom of a hydroxyl group for example an acid chloride or acid anhydride such as acetic anhydride, succinic anhydride, maleic anhydride, and ortho-sulphobenzoic anhydride, a sulphonyl chloride, isocyanates or unsaturated alkylating compounds, e.g. a vinyl compound such as acrylonitrile and methacrylonitrile.
• an acid chloride or acid anhydride such as acetic anhydride, succinic anhydride, maleic anhydride, and ortho-sulphobenzoic anhydride, a sulphonyl chloride, isocyanates or unsaturated alkylating compounds, e.g. a vinyl compound such as acrylonitrile and methacrylonitrile.
• the reaction product of the said hydroxyl containing polymer with maleic anhydride may further be allowed to react with a bisulphite thus forming a bisulphite addition product.
• the bisulphite used is preferably an alkali metal bisulphite.
• the compounds used according to the present invention can be present in the developer bath or can be added to the coating composition of a silver halide emulsion layer and/or incorporated into a water-permeable layer which when coated under or on top of the emulsion layer forms a water-permeable system with the silver halide emulsion layer and is then in effective contact with the silver halide.
• the compounds of use according to the invention can be incorporated into the coated emulsion layer either by treating the emulsion layer with an aqueous solution of these compounds or by coating this layer with a waterpermeable layer containing the said compounds, or also by bringing the said compounds from a water-permeable layer lying under the emulsion layer and comprising said compounds by diffusioninto effective contact with the silver halide.
• the water-soluble compounds of the invention 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 therein as a 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 another moment preceding the application of the emulsion.
• the polyaddition compounds of the invention are preferably added to the silver halide emulsion composition after the chemical ripening process and just before coating the emulsion.
• the polyaddition compounds are preferably added from a solution in water or in an aqueous mixture of water and water-miscible organic solvents such as ethanol that do not impair the photographic properties of the light-sensitive silver halide emulsion.
• the optimum amount of polyaddition compound added to the silver halide emulsion depends on the compound itself on the nature of the colloid binding agent for the silver halide grains, and on the amount and the kind of the silver halide in the emulsion. In general, however, the polyaddition compounds are added to the light-sensitive material in amounts ranging from 10 mg. to 10 g. per mole of silver halide. In the developing bath they are normally used in amounts ranging from 10 mg. to 5 g. per liter. If necessary, these compounds can also be added in amounts exceeding these limits.
• the step of influencing the sensitometric characteristics of silver halide emulsions by means of the polyaddition compounds of the invention can be combined with a method known as chemical sensitization, in which together with the above-mentioned polyaddition compounds chemical sensitizers are used, e.g., sulphur-containing compounds such as allyl isothiocyanate, allylthiourea or sodium thiosulphate, reducing compounds such as the tin compounds described in the Belgian patent specifications 493,464 filed Jan.
• chemical sensitizers e.g., sulphur-containing compounds such as allyl isothiocyanate, allylthiourea or sodium thiosulphate, reducing compounds such as the tin compounds described in the Belgian patent specifications 493,464 filed Jan.
• the polyaddition compounds employed 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 such as those described in Belgian patent specifications 524,121 filed Nov. 7, 1953 by Kodak Co. and 677,337 filed Mar. 4, 1966 by Gevaert-Agfa N.V. and in published Dutch patent application 6715932 filed Nov. 23, 1967 by Gevaert- Agfa N.V.
• organic onium compounds and polyonium compounds preferably of the ammonium or sulphonium type, e.g. quaternary tetraalkylammonium salts, alkylpyridinium salts, bisalkylene-pyridinium salts, alkylquinolinine salts, trialkylsulphonium salts, onium derivatives of amino-N-oxides as described in United Kingdom patent specification 1,121,- 696 filed Oct.
• Gevaert-Agfa N.V. and iodonium compounds for instance diphenyl iodonium chloride as described in United Kingdom patent specification 1,119; 075 filed Oct. 7, 1965 By Gevaert-Agfa N.V. can be used together with the polyaddition compounds according to the invention in the developing solution as well as in the light-sensitive material.
• Other ingredients such as colour couplers, developing substances, hardening agents, plasticizers, and Wetting agents, can also be added to the emulsion in the ordinary way.
• polyaddition compounds of the invention are also particularly suitable for the development of silver chloride and silver chlorobromide emulsions comprising at most 50 mole percent of silver bromide for reproducing line and screen-images with hydroquinone formaldehyde bisulphite developers.
• the values 3 I and II given for the speed are relative values corresponding to a density 0.1 and 1 respectively above the fog Exampclle g g g dlfference that the value; the value of 100 was given to the speed values I compoun s m t e ta 6 e 0W were added as and II of the freshly prepared material comprising no Velophlent acceleratofsdevelopment accelerating compound. The followmg results were attamed.
• a process for developing an exposed photographic material containing light-sensitive silver halide wherein the development is carried out with a water-soluble polymeric compound obtained by polyaddition of a dihydric alcohol corresponding to the formula:
• X stands for arylene, a straight-chain or branched-chain alkylene, alkenylene or alkynylene group which has from 2 to 8 C-atoms, cycloalkylene or alkylene-cycloalkylene, with a bisepoxide corresponding to the formula:
• Z stands for a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms, being present in the development medium.
• X stands for arylene, a straight-chain or branched-chain alkylene, alkenylene or alkynylene group which has from 2 to 8 C-atoms, cycloalkylene or alkylene-cycloalkylene,
• Z stands for a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms
• a photographic light-sensitive material which comprises a silver halide emulsion layer or a water-permeable layer adjacent to a silver halide emulsion layer containing a water-soluble polymeric compound obtained by polyaddition of a dihydric alcohol correspondinng to the formula:
• X stands for arylene, a straight-chain or branched-chain alkylene, alkenylene or alkynylene group which has from 2 to 8 C-atoms, cycloalkylene or alkylene-cycloalkylene,
• Z stands for a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms.
• X stands for arylene, a straight-chain or branched-chain alkylene, alkenylene or alkynylene group which has from 2 to *8 C-atoms, cycloalkylene or alkylene-cycloalkylene,
• Z stands for a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms
• a photographic material according to claim 5, wherein the said silver halide emulsion is a silver chloride emulsion or a silver chlorobromide emulsion, which comprises at most 50 mole percent of bromide, suitable for the production of line and screen prints.
• a photographic developing composition comprising a silver halide developing agent and a water-soluble polymeric compound obtained by polyaddition of a dihydric alcohol corresponding to the formula:
• X stands for arylene, a straight-chain or branched-chain alkylene, alkenylene or alkynylenegroup which has from 2 to 8 C-atoms, cycloalkylene or alkylene-cycloalkylene,
• a photographic developing composition according to claim 10 wherein: Z stands for a straight-chain or branched-chain alkylene group which has for 2 to 8 C-atoms.
• the said polymeric compound comprises recurring units of the following structure:
• X stands for arylene, a straight-chain or branched-chain alkylene, alkenylene or alkynylene group which has from 2 to 8 C-atorns, cycloalkylene or alkylene-cycloalkylene,
• Z stands for a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms
• a photographic developing composition according to claim 10 comprising hydroquinone and formaldehyde bisulphite.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Physics & Mathematics (AREA)
• Organic Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=10275058

Family Applications (1)

Country Status (5)

Cited By (5)

Families Citing this family (2)

• 1970
  • 1970-06-11 GB GB2480270A patent/GB1346599A/en not_active Expired
• 1971
  • 1971-05-17 US US00144234A patent/US3746545A/en not_active Expired - Lifetime
  • 1971-05-19 CA CA113414A patent/CA986642A/en not_active Expired
  • 1971-06-08 FR FR7120822A patent/FR2096094A5/fr not_active Expired
  • 1971-06-11 BE BE768366A patent/BE768366A/nl unknown

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