Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01P—MEASURING LINEAR OR ANGULAR SPEED, ACCELERATION, DECELERATION, OR SHOCK; INDICATING PRESENCE, ABSENCE, OR DIRECTION, OF MOVEMENT
  • G01P1/00—Details of instruments
  • G01P1/12—Recording devices
  • G01P1/122—Speed recorders
• • 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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
  • G03C8/06—Silver salt diffusion transfer
• • 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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/24—Photosensitive materials characterised by the image-receiving section
  • G03C8/26—Image-receiving layers

Definitions

• the present invention relates to the silver complex diffusion transfer process of producing images and more especially to an accelerated process.
• a light-sensitive silver halide emulsion layer is exposed to an image and then pressed while in wet condition into contact with a specially prepared receiving material in the presence of developer and a substance or substances which dissolve the silver halide in complexed form.
• the exposed image areas are developed and do not undergo any further change.
• the undeveloped silver halide in the unexposed areas is complexed or solubilized by a compound or compounds present in the liquid or in the receiving material, transferred by diffusion into the receiving layer of the said image-receiving material and converted therein to metallic silver.
• the conversion is promoted by the catalytic action of developing nuclei.
• the developing nuclei normally consist of finely divided metal or metal sulphide. They can be incorporated in the image-receiving material during its manufacture or formed in situ therein during the diffusion transfer process.
• Such a process has various advantages, for instance, a longer shelf life for the processing bath and a more permanent quality of the white color of the obtained copies.
• the process according to the said British patent specification possesses the disadvantages of a delay of the diffusion transfer image formation and of the formation of fog in the light-sensitive material which probably isv due to the nonmigratory developing substances present.
• the said process can be carried out by wetting only the light-sensitive material with treating liquid and then pressing it against a dry image-receiving material when using a light-sensitive material which comprises in addition to the light-sensitive silver halide emulsion layer a water-permeable top layer from which at least a thin stratum is transferred to the image-receiving material when separating said both materials.
• the secondary developing substance is a poor developing substance in itself so that it cannot produce fog in the light-sensitive material, whereas the superadditive combination has a so surprisingly rapid effect that the diffusion transfer process according to this invention occurs as rapid as in a process wherein the developing substances are incorporated in the bath. Further, a process according to this invention possesses the advantages already cited above of a diffusion transfer process without developing substances in the processing bath.
• 3-pyrazolidone compounds which are suited for being used according to this invention mostly correspond to the following general formula:
• R represents an aryl radical or a substituted arvl radical
• R represents a hydrogen atom or an acyl radical such as an acetyl radical, and a each of R R R and R (the same or different) repreresents a hydrogen atom, an alkyl radical, a substituted alkyl radical, an aryl radical or a substituted aryl radical.
• basic compounds are added such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium carbonate, sodium phosphate, etc.
• anhydrous salt for a compound which is weak in this respect, e.g. sodium phosphate, it is appropriate to use an amount of the anhydrous salt of from 50 to 200 g. per liter. In the case of a compound which imparts a high degree of alkalinity, eg sodium hydroxide, an amount of from 5 to 20 g. will suffice.
• Anyhydrous sodium sulfite may be incorporated into the processing liquid in an amount e.g. of from 10 to 40 g. per liter.
• the processing liquid may further contain other usual ingredients such as sodium bromide, calcium sequestering compounds and black-toning agents e.g. l-phenyl-S- mercaptotetrazole or similar products such as those described in the British patent specification 561,875 and the Belgian patent specification 502,525, but need not contain any developer substance.
• other usual ingredients such as sodium bromide, calcium sequestering compounds and black-toning agents e.g. l-phenyl-S- mercaptotetrazole or similar products such as those described in the British patent specification 561,875 and the Belgian patent specification 502,525, but need not contain any developer substance.
• An image-receiving material according to the invention may e.g. consist of a support which is impregnated with development nuclei or with a substance or substances for forming such nuclei in situ.
• an image-receiving material for being used in a process according to this invention comprises a non-light-sensitive colloid layer for instance a water-permeable organic colloid layer such as a gelatin layer, on a paper or other support, the colloid layer incorporating the development nuclei or substances which can form such nuclei in situ during the diffusion transfer process.
• nuclei for complexed silver halide nuclei for physical development as well as ingredients for chemical image formation are meant.
• Development nuclei for silver halide complexes suitable for promoting the formation of the silver containing image in the image-receiving layer are the sulfides of heavy metals e.g. of antimony, bismuth, cadmium, cobalt, lead, nickel, silver and zinc.
• Selenides, polysulfides, polyselenides, mercaptans, stannous halides, heavy metals or their salts and fogged silver halides are also suitable for this purpose.
• the complex salts of lead sulfide and zinc sulfide are effective either in themselves or mixed with thioacetamide, dithiobiuret and dithiooxamide.
• the heavy metals silver gold, platinum, palladium and mercury are to be mentioned, preferably in their colloidal form. The noble metals among them are the most active.
• the image-receiving layer and/ or a layer which is in effective contact with this image-receiving layer incorporate hydroquinone as a principal developing substance.
• the imagereceiving material may comprise at least one compound selected from the group consisting of alkali metabisulfites such as potassium metabisulfite, water-soluble inorganic bisulfites and water-soluble aldehyde bisulfites.
• alkali metabisulfites such as potassium metabisulfite
• water-soluble inorganic bisulfites water-soluble aldehyde bisulfites.
• aldehyde bisulfites Such an image-receiving material is described in the German patent specification 1,129,052.
• the image-receiving material may also contain usual ingredients such as sodium sulfite, a complexing agent for silver halide such as sodium thiosulfate and black-toning agents such as those mentioned above.
• the image-receiving material is prepared by coating onto a support, mostly of paper, a thin imagereceiving layer from an aqueous suspension containing developing nuclei for complexed silver halide and which mostly is coated in such a way that per sq. m. of support from 1 to g. of gelatin or other water-permeable binding agent, from 0.1 to 5 g. of hydroquinone, from 0.5 to 5 g. of anhydrous sodium thiosulfate and from 0.2 to 2 g. of at least one compound selected from the group consisting of alkali metabisulfites, water-soluble inorganic bisulfites and water-soluble aldehyde bisulfites are present.
• the light-sensitive material comprises a silver halide emulsion layer and this emulsion layer and/ or a waterpermeable layer which is in effective contact with said emulsion layer usually incorporates such an amount of a 3-pyrazolidone developing compound, that from 0.05 to 0.5 g. of that developing substance are present per sq. m. Occasionally other ingredients such as black-toning agents may also be present in the light-sensitive material.
• the emulsion composition is that of a conventionally used emulsion in the art of difiifusion transfer.
• the emulsion composition is not critical provided its silver salt(s) is (are) capable of development and diffusion in the exposed and non-exposed areas respectively with the rapidity required in diffusion transfer processes.
• Silver chloride emulsions which may contain silver bromide or silver iodide, and to which other ingredients have been added so as to impart the desired emulsion characteristics are preferably used. Any such emulsion can be unhardened or slightly hardened.
• the light-sensitive material and/ or the imagereceiving material contains in the uppermost layer (1) at least one water-insoluble metal alginate as described in the French patent specification 1,304,279, or (2) the chromium salt of carboxymethyl cellulose either or not together with at least one water-insoluble metal alginate as described in the French patent specification 1,304,280.
• the primary and secondary development stages are caused to proceed so rapidly, that in the most modern developing apparatus for quick treatment very good images are obtained. This is surprising, since the primary and secondary development stages can only proceed when the image-receiving and light-sensitive materials are pressed together by the rollers of the developing apparatus, as the processing liquid most-1y does not contain developing substances and as the developing substances present in the light-sensitive material cause only an initial primary development.
• a light-sensitive material containing 1-phenyl-3-pyrazolidone and comprising as top layer a layer for instance of poly(acrylamide) is image-wise exposed and then wetted with treating liquid for instance in the presence of developing substances and of a complexing agent for silver halide.
• treating liquid for instance in the presence of developing substances and of a complexing agent for silver halide.
• This may occur in different ways for instance by dipping the light-sensitive material in the treating liquid, by moistening it at one side with treating liquid etc.
• the light-sensitive material thus treated is then pressed against a dry image-receiving material consisting of a baryta-coated paper support to which a layer containing development nuclei and hydroquinone is applied.
• bot-h materials are separated and a diffusion transfer image of excellent quality is obtained on the image-receiving material.
• Suitable binding agents for the top layer, from which at least a thin stratum is transferred to the image-receiving material are for instance the following water-permeable colloids: methyl cellulose, the sodium salt of carboxy methyl cellulose, hydroxy ethyl cellulose, hydroxy ethyl starch, hydroxy propyl starch, sodium alginate, gum tragacanth, starch, poly(vinylalcohol), poly(acrylic acid), poly(acryl amide), poly(vinyl pyrrolidone), poly(oxyethylene), copoly( methyl vinyl ether/ maleic acid) etc.
• the thickness of this top layer varies among others according to the nature of the colloid chosen and the viscosity of the used colloid solution.
• the water-permeable top layer is preferably not hardened, and may contain the same ingredients which may be present in the other layers of the light-sensitive material.
• the diffusion transfer process with a light-sensitive material comprising a top layer from which at least a stratum is transferred to the image-receiving material should also be read in conjunction with the patent application filed on even date herewith for Improved Silver Salt Diffusion Transfer Process.
• a light-sensitive material comprising a top layer from which at least a stratum is transferred to the image-receiving material
• Example 1 Water cm. 877.2 Gelatin g 40 aqueous sodium sulfide cm. 2.4 10% aqueous cobalt nitrate cm. 13.2 iPotassium metabisulfite g 12.8 Hydroquinone g 6.4 Sodium thiosulfate g 48 This suspension is cast in such a way that 1 liter 12 sq. m. of support are covered.
• the light-sensitive material is now image-wise exposed and together with the image-receiving material passed through a diffusion transfer developing apparatus containing a solution of the following composition:
• Example 2 A light-sensitive material is prepared by coating onto a paper support of 90 g./sq. m. a gelatino silver chloride emulsion in such a way that 1.33 g. of silver chloride is present per sq. m. of light-sensitive material. This lightsensitive layer is coated over with a top layer from the following solution in a proportion of 1 litre per 10 sq. m.:
• PAM 75 (trade name for a polyacrylamide of medium viscosity range marketed by American Cyanamid Company, New York, N.Y., U.S.A.) sg 10 10% solution of 1-phenyl-3-pyrazolidone in ethanol cm. 100 10% aqueous saponine cm. 10
• the dispersion of cobalt (II) sulfide is prepared at 45 C. from:
• the materials are then separated from each other.
• the same light-sensitive material can be used now for the production of several positive copies by wetting it again and again with treating liquid, pressing it together with an image-receiving material and then separating it therefrom.
• the light-sensitive material wetted with treating liquid can also be pressed together with the dry image-receiving material whilst heat is supplied, for instance by feeding both materials between heated rollers or by first contacting them as usual and thereupon guiding them between heated rollers.
• heat is supplied, for instance by feeding both materials between heated rollers or by first contacting them as usual and thereupon guiding them between heated rollers.
• German utility model 1,794,536 According to these different embodiments with supply of heat, a completely dry positive copy as well as a completely dry negative copy of the original are obtained which even are not to be separated mechanically as they become detached by their own.
• Example 3 Example 1 is repeated but by using a light-sensitive material which instead of being coated over with a layer containing PAM 75 (trade-name) is coated over with a top layer from the following solution in a proportion of What I claim is:
• a process for obtaining photographic images according to the silver complex diffusion transfer process comprising image-wise exposing a light-sensitive material comprising a silver halide emulsion layer and a 3-pyrazoli-- done developing compound, bringing said light-sensitive material in the presence of an alkaline processing liquid into contact with an image-receiving material containing hydroquinone and a member selected from the group consisting of development nuclei and substance capable of forming such nuclei in situ, and separating said materials from each other.
• R is a member selected from the group consisting of an aryl radical and a substituted aryl radical
• R is a member selected from the group consisting of a hydrogen atom and an acyl radical
• each of R R R and R is a member selected from the group consisting of a hydrogen atom, an alkyl radical, a substituted alkyl radical, an aryl radical and a substituted aryl radical.
• the imagereceiving material comprises at least one compound selected from the group consisting of alkali metabisulfites, water-soluble inorganic bisulfites and water-soluble aldehyde bisulfites.
• processing liquid comprises sodium phosphate and sodium sulfite.
• a process for obtaining photographic images according to the silver halide diffusion transfer process which comprises image-wise exposing a light-sensitive material comprising a silver halide emulsion layer and bringing this light-sensitive material, in the presence of an alkaline processing liquid, into contact with an image-receiving material containing development nuclei and/or substances capable of forming such nuclei in situ, whereafter these materials are separated from each other, wherein the image-receiving material contains hydroquinone and the light-sensitive material contains a 3-pyrazolidone developing compound, characterized thereby that as a top layer on the light-sensitive material a water-permeable layer is applied from which at least a thin stratum is transferred to the image-receiving material when separating said both materials.
• the imagereceiving material comprises a support and a top layer containing a binding agent, a filler and hydroquinone.
• top layer contains development nuclei and/or substances capable of forming such nuclei.
• top layer contains a protein as a binding agent.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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Citations (5)

• 0
  • GB GB1054252D patent/GB1054252A/en active Active
  • NL NL281744D patent/NL281744A/xx unknown
  • GB GB1054253D patent/GB1054253A/en not_active Expired
  • BE BE635813D patent/BE635813A/xx unknown
  • BE BE635812D patent/BE635812A/xx unknown
  • BE BE633674D patent/BE633674A/xx unknown
• 1963
  • 1963-06-13 SE SE6549/63A patent/SE316371B/xx unknown
  • 1963-06-14 CH CH740663A patent/CH405073A/fr unknown
  • 1963-06-15 FR FR938253A patent/FR1362792A/fr not_active Expired
  • 1963-06-15 DE DEG37965A patent/DE1259200B/de active Pending
  • 1963-06-17 GB GB24043/63A patent/GB1042477A/en not_active Expired
  • 1963-08-05 SE SE08614/63A patent/SE335674B/xx unknown
  • 1963-08-05 US US300101A patent/US3335007A/en not_active Expired - Lifetime
  • 1963-08-05 CH CH965263A patent/CH442004A/de unknown

Patent Citations (5)

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