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
  • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
  • G03C1/725—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing inorganic compounds
  • G03C1/7253—Lead salts
• • 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
  • G03C1/705—Compositions containing chalcogenides, metals or alloys thereof, as photosensitive substances, e.g. photodope systems

Definitions

• Preferred lead salts are lead iodide, lead bromide, or a crystalline mixture thereof.
• a sensitizing agent may be added to increase the photosensitivity of the lead salt. Faint print-out images may be intensified by treatment with a physical development using, for instance, a solution containing a reducing agent and metal ions of a metal more electropositive than lead.
• the present invention relates to photographic materials suited for image formation by printingout and that are of the non-silver halide type.
• lead compounds such as lead iodide, lead azide or lead bromide have proved to be valuable as described, e.g., in the US. patent specification 2,414,839.
• photosensitive lead salts preferably lead iodide and lead bromide offer a valuable print-out sensitivity when dispersed in an organophilic binder or binder system.
• the present invention provides a new photosensitive recording material comprising a photosensitive lead salt such as lead bromide, lead iodide or a crystalline mixture of lead iodide and lead bromide dispersed in an orgauophilic binder or binder system.
• organophilic binder or binder system is meant a binding agent or mixture of binding agents, which is soluble in an organic solvent, e.g. alcohols preferably lower alcohols such as methanol and ethanol, aliphatic carboxylic acid esters and aliphatic ketones.
• print-out is meant the formation of a visible image by exposure to active radiation including electromagnetic radiation and ionizing radiation, e.g. 8- radiation, without the aid of a further development.
• the exposure of the photosensitive article according to the present invention may proceed in dry or wet state. Wetting preferably occurs with a lower aliphatic alcohol, e.g. methanol.
• the lead salts can be sensitized by means of so-called chemical sensitizers.
• a first group of these sensitizing agents are sulphur compounds or compounds wherein sulphur has been replaced by selenium or tellurium.
• those sulphur, selenium or tellurium compounds are used that possess reducing properties and/or that contain a releaseable sulphur, selenium or tellurium atom, i.e. a sulphur, selenium or tellurium atom that is easily split 3,59%,886 Patented Sept. 12, 1972 Ice off e.g. by heating.
• thiol compounds or thiolates (2) compound corresponding to the following structural HOCHr-[S-O" ions, MO-SO- ions, wherein M is a cation, or S02- ions derived from the hypothetical sulfoxylic acid S(OH) (6) compounds yielding R--SO -S, R.CO.S", R.CS.S- or R.SC.O-' ions, wherein R is an organic group, e.g. an alkyl group such as a methyl group, a substituted alkylgroup, an aryl group or a substituted aryl group,
• xanthates i.e. salts of xanthic acid having the general formula R O.CS.SM, wherein M is a cation, e.g. an alkali metal cation, and R is an alkyl or substituted alkyl radical, e.g. a benzyl radical.
• the light-sensitive compounds may be treated with the chemical sensitizers before, at the same time of or after coating the photosensitive composition to a support. Preferably they are added to the coating composition before coating and intimately mixed therewith, so that a chemical interaction can take place already before coating and storage. According to a particular embodiment the recording material is exposed while still being wet after the treatment with a solution containing a chemical sensitizing agent.
• the chemical sensitizing agents may be used in a rather large amount, e.g. in a ratio by weight up to 1:2 in respect of the light-sensitive lead salt, preferably in a range of
• cyanine dyes can be used e.g. the dyes having the formulae:
• organophilic binding agents particularly suited for use according to the present invention are mentioned sucrose benzoate and poly(vinyl-butyral), ethylcellulose, shellac, polyvinyl stearate, copoly(viny1 acetate/N-vinylpyrrolidone), and copoly(methacrylic acid/methyl methacrylate).
• the ratio by weight of binding agent or mixture of binding agents to light-sensitive lead salt is preferably between 9:1 and 1:3.
• the amount of light-sensitive lead salt per sq. m. can vary within wide limits but prefer- 7 5 ably amounts to at least 1 g. per sq. m.
• the preferably used lead iodide and lead bromide can be freshly prepared in finely divided state from a watersoluble lead compound, e.g. lead acetate, and a halide ion-releasing compound, e.g. sodium iodide.
• a watersoluble lead compound e.g. lead acetate
• a halide ion-releasing compound e.g. sodium iodide.
• the precipitate of light-sensitive lead salt is freed from water before use.
• Mixtures of light-sensitive lead salts (crystalline mixtures), can be prepared by coprecipitation.
• the grain size of the applied lead salts is preferably between 0.03 and about micron.
• the organic solvents used in the application of the coating composition are preferably anhydrous, although they may be polar or miscible with water such as methanol.
• the boiling point of said solvents is preferably not higher than 100 C. in order to enable an easy removal of the solvent after the recording layer has been coated.
• the print-out images are relatively stable to daylight. They can be stored for at least two weeks in dimmed daylight. The stability in daylight can be increased by applying to the print-out images U.V. light-absorbing substances.
• the recording materials of the present invention are suitable for the reproduction of line work as well as for the reproduction of continuous tone originals and for the recording of signals as are obtained from modulated spot recording systems and recording systems wherein penetrating rays such as X-rays, beta-rays or gamma-rays are applied.
• a water-permeable binding agent e.g. ethyl-cellulose or polyvinyl-n-butyral
• an image-intensification technique may be applied.
• a print-out image which has to be considered as a latent image, can be developed and made clearly visible by means of an aqueous liquid, which may contain a water-miscible organic solvent.
• a so-called physical developer may be used.
• the intensification or development of the latent image by means of a redox-system containing a reducing agent and ions of a metal that is more electropositive than lead and/or ions e.g. of dyestuffs or leuco compounds having a redox potential not lower than that of said ions is called here a physical development. So, the development can be carried out with ions of methylene blue, silver ions, mercury(II) ions, mercury(I) ions, copper(II) ions or copper (I) ions in the presence of a reducing agent, e.g. p-aminophenol, 1-phenyl-3-pyrazolidinone or ascorbic acid.
• a reducing agent e.g. p-aminophenol, 1-phenyl-3-pyrazolidinone or ascorbic acid.
• the latent image which according to some theoretical considerations is presumed to consist of lead or lead sulphide nuclei, is successively treated with a silver nitrate solution and a solution containing a reducing agent for silver ions.
• the silver image obtained in this way is fixed or stabilized.
• the stabilization which in principle consists of the conversion in the recording material of light-sensitive salts in non-light-sensitive salts, may be effected by a short treatment (2 or 3 see.) with an aqueous solution containing thiosulphate ions, e.g. originating from sodium thiosulphate, or with isothiocyanate ions, e.g. originating from sodium isothiocyanate.
• stabilizing compositions contain dissolved halide ions e.g. originating from ammonium fluoride and ammonium chloride, and/or contain a watersoluble carboxylic acid e.g. acetic acid.
• the stabilizing or fixing solutions may contain watersoluble sulphites or hydrogen sulphites to prevent yellowing of the fixed image by oxidation of the developer.
• Fixation may be carried out by treating the physically developed material for a larger time than in stabilization with a solution containing ammonium chloride and thio sulphate ions or other known silver ion-complexing agents dissolving the light-sesitive salts and transferring them to the fixing bath.
• the more electropositive metal ions and the reducing agent are preferably kept in separate solutions in order to avoid alteration of the developing bath.
• the physical developing composition need not to be alkaline. So, the pH thereof will preferably be kept below 7.
• Suitable developing compositions for physical development are described in the Belgian patent specification 662,491 and the United Kingdom patent specification 1,043,250.
• wetting agents e.g. ethanol, ethylene glycol and non-ionic, anionic or cationic surfactants.
• EXAMPLE 1 60 g. of sucrose benzoate and 75 g. of lead(II) bromide were ball-milled for 12 h. in 190 g. of methanol. The suspension obtained was then diluted with 300 g. of methanol and in a proportion of g./sq.m. applied to a support. After drying, the light-sensitive material thus obtained was exposed for 60 sec. through a transparent negative by means of a Philips HP 80 lamp placed at a distance of 25 cm. A greyish-black positive copy on White background was obtained.
• EXAMPLE 2 20 g. of poly(vinyl-n-butyral) and 75 g. of lead(II) bromide were ball-milled for 12 h. in 230 g. of methanol. To the suspension thus obtained a solution of 15 g. of Rongal HT type 66 (trade name of Badische Anilin- & Soda-Fabrik, Ludwigshafen, Germany, for the addition product of formaldehyde and sodium dithionate) in 300 g. of methanol was added. The suspension formed was applied in proportion of g./sq.m to a paper support. After drying, the material was image-wise exposed for 15 sec. by means of a w. xenon lamp placed at a distance of 5 cm. A greyish-black copy on white background was obtained.
• Rongal HT type 66 trade name of Badische Anilin- & Soda-Fabrik, Ludwigshafen, Germany
• EXAMPLE 3 40 g. of poly(vinyl-n-butyral) and 150 g. of lead(II) iodide were ball-milled for 12 h. in 460 g. of methanol. To the suspension obtained a solution was added of 30 g. of mercaptoacetic acid in 350 g. of methanol. The suspension formed was applied to a paper support at a rate of 100 g. per sq.m. After drying, the material was exposed through a transparent negative in a Buroza 600 apparatus (trade name of Atlas, Delft, Netherlands, for a diazoprint apparatus), at a travelling speed of 30 cm./ min. A greyish-black positive print-out copy was obtained on a yellow background.
• Buroza 600 apparatus trade name of Atlas, Delft, Netherlands, for a diazoprint apparatus
• EXAMPLE 4 40 g. of poly(vinyl-n-butyral) and 150 g. of lea l(ll) bromide were ball-milled for 12 h. in 460 g. of methanol. The suspension obtained was then applied to a paper support at a rate of 100 g./sq.m. After drying, this material was dipped in a 2% solution of 2,3-dimercapto-lpropanol in methanol, and when still wet exposed imagewise for 60 see. by means of a Philips HP 80 lamp. A greyish-black image on a white background was obtained.
• EXAMPLE 5 40 g. of poly(vinyl-n-butyral) and 150 g. of lead(II) bromide were ball-milled for 12 h. in 360 g. of methanol. The suspension obtained was diluted with 350 g. of methanol and coated onto a paper base in a proportion of 50 g. per sq.m. After drying, the material was exposed through a transparent negative in a Buroza 600 (trade name) diazo printing apparatus at a traveling speed of 8 cm./sec. The exposed material showing no visible image was successively dipped in the following baths:
• the material After rinsing and drying, the material showed a positive brown silver image.
• EXAMPLE 8 150 g. of lead(II) bromide were ball-milled for 12 h. in a solution containing 34 g. of poly(vinyl-n-butyral) and -6 g. of poly(N-vinylpyrrolidone) in 460 g. of methanol. To the suspension obtained a solution was added containing 2 g. of l-ascorbic acid and 1 g. of citric acid in 32 g. of methanol. This suspension was applied to a paper support in a proportion of 150 g./sq.m. After drying, the light-sensitive material obtained was image-wise exposed in a Buroza 600 (trade name) apparatus at a copying speed of 2 cm./sec. The exposed material showing only a faint image was then successively dipped in the following baths:
• EXAMPLE 19 4 g. of poly(vinyl-n-butyral) and 15 g. of lead(II) iodide were ball-milled for 12 h. in 46 g. of methanol. The suspesion obtained was then applied to a paper support at a rate of 23 g. of lead(II) iodide/sq. 111. After drying, this material was dipped in a 2% solution of potassium metaarsenite (KAsO in methanol, and when still wet exposed image-wise for 60 sec. by means of a Philips HP 80 lamp. A black image on a yellow background was obtained.
• K metaarsenite K metaarsenite
• Example 19 was repeated with the difference, however, that the solution of potassium metaarsenite was replaced by a solution of (H C) CNH -BH .A black image was obtained.
• EXAMPLE 21 3 g. of poly(vinyl-nbutyral) and 5 g. of lead(II) bromide were ball-milled for 12 h. in 47 g. of methanol. To the suspension obtained a solution was added of 2 g. of l-ascorbic acid in 23 g. of methanol. This suspension was applied to a paper support at a rate of 4 g. of lead (II) bromide/sq. in. After drying, the material was exposed through a transparent negative in a Buroza 600 (trade name) apparatus at a speed of 2 cm./sec. The exposed material showing only a faint image was then successively dipped in the following bath:
• a print-out process for recording information comprising the step of information-wise exposing to active radiation a photosensitive recording material comprising a layer incorporating a photosensitive lead halide salt dispersed in an organophilic binder in a ratio by weight of l/9 to 3/1 of salt to binder, the amount of said salt being at least 1 g./sq.m. of layer area, said exposure being for a time suificient to produce in said photosensitive layer a visible image, said lead salt being sensitized with (1) a compound of the group consisting of:
• xanthates i.e., salts of Xanthic acid having the general formula R O.CS.SM, wherein M is a cation and R is an alkyl radical, or
• photosensitive lead salt is lead iodide or lead bromide, or a crystalline mixture thereof.
• organophilic binding agent is selected from the group consisting of sucrose benzoate, poly (vinyln-butyral) ethylcellulose, shellac, polyvinyl stearate, copoly(vinyl acetate/N-vinylpyrrolidone) and copoly(methacrylic acid/ methyl methacrylate).
• a process according to claim 8 wherein the said ions are silver ions, mercury(II) ions, mercury(I) ions, copper(H) ions or copper(I) ions.

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

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• 1968
  • 1968-11-12 GB GB53668/68A patent/GB1283038A/en not_active Expired
• 1969
  • 1969-11-10 BE BE741484D patent/BE741484A/xx unknown
  • 1969-11-11 DE DE19691956513 patent/DE1956513A1/de active Pending
  • 1969-11-12 FR FR6939334A patent/FR2023139A1/fr not_active Withdrawn
  • 1969-11-12 US US876064A patent/US3690886A/en not_active Expired - Lifetime

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