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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/262—Processes using silver-salt-containing photosensitive materials or agents therefor using materials covered by groups G03C1/42 and G03C1/43
• • 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
  • G03C1/42—Developers or their precursors
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/15—Lithographic emulsion

Definitions

• ABSTRACT A method is described of producing high-contrast images by exposure and development of a photographic lith-type silver halide material wherein the lith material incorporates hydroquinone and development occurs by treating the exposed material with an alkaline development activator in the presence of hydroxylamine or a N-mono-substituted hydroxylamine. Processing time is reduced and the processing composition can be used for extended periods of time without replenishment Favourable dot quality can be obtained.
• the present invention relates to processing of exposed high-contrast silver halide materials for graphic arts use and particularly to processing of photographic silver halide materials of the lith type wherein the hydroquinone developing agent is incorporated into the said material.
• Lith-type emulsions are high-contrast fine-grain silver halide emulsions containing at least about 50 mole percent of silver chloride and at least about 5 mole percent of silver bromide. If desired they may comprise up to about 5 mole percent of silver iodide but generally the iodide content is less than about 1 mole percent. They have a characteristic curve with short toe and high-gamma and produce sharply defined images with high density extending to. the edges of lines and dots. This applies especially when a developer with so-called lith-effect is used.
• these lith-type developers comprise hydroquinone as the sole developing agent and have a very' low sulphite ion content, which is maintained at a low and constant value by the addition to the sulphite containing developing solution of formalin (paraformaldehyde) or by the direct addition to the solution of the addition product of sulphite and formalin namely sodium formaldehyde hydrogen sulphite.
• formalin paraformaldehyde
• Another object of the present invention is to provide a processing composition for lithtype silver halide ele-, ments that is less liable to exhaustion and can be used for extended periods of time without replenishment.
• R represents hydrogen, alkyl, e.g., methyl, ethyl, propyl, isopropyl, octyl, decyl, dodecyl, etc. in.-
• substituted alkyl e.g., alkyl substitutedibyanyl such as phenyl, hydroxy, carboxyl, sulpho, amino, sub.- stituted amino, and NHOH, or aryl including substituted aryl e.g., aryl substituted. by. halogen, alkyl; alkoxy, hydroxy, carboxyl, sulpho, alkoxycarbonyl, amino and substituted amino.
• addition salts of the hydroxylamine compounds may also be used in thisinvention which include, for. example,,sulphates, phosphates, carbonates, oxalates, acetates .andzchlorides. 0f
• the acid salt used should have no detrimental effect on the photographic material.
• hydroxylamine compounds for use according to the present invention are. hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine, N-propylhydroxylamine, N-ysulphopropylhydroxylamine, N-a-carboxypropylhydroxylamine, N-isopropylhydroxylamine, N-pheny-lhydroxylamine, a-hydroxylaminovfifphenyl propionic acid, N p-carboxyphenylhydrox-ylamine, N-pmethoxy-phenylhydroxylamine, N-mssulphophenylhydroxylamine, and
• the present invention thus provides a method of pro: ducing high-contrast images by exposure and development of a photographic lith-type silver halide material, wherein said lith-type material incorporates hydroquinone as developing agent and development is effected by treatment of the exposed material with an alkaline development activator in the presence of hydroxylamine or a N-mono-substituted hydroxylamine.
• a lith-type silver halide material comprises a silver halide emulsion layer containing at least about 50 mole percent, preferably at least about 70 mole percent of silver chloride, at least about 5 mole percent of silver bromide and from to about mole percent of silver iodide.
• the average grain diameter is preferably comprised between about 0.1 and about 0.4 micron.
• the hydroxylamine compound may be present in the alkaline solution or in the photographic lith-type material or in both. Therefore, the present invention also provides a photographic silver halide material as defined above containing hydroquinone which comprises in the said silver halide emulsion layer and/or in a hydrophilic colloid layer in water-permeable relationship therewith hydroxylamine or a N-monosubstituted hydroxylamine.
• the hydroquinone developing agent should be in effective contact or relationship with the silver halide, which means that it should be present in the silver halide emulsion layer itself and/or in one or more other hydrophilic colloid layers in water-permeable relationship with the silver halide emulsion layer e.g., a hydrophilic colloid intermediate layer arranged between the support and the silver halide emulsion layer or a hydrophilic colloid layer coated over the silver halide emulsion layer.
• the alkaline development activator is normally free of hydroquinone developing agent. However, when the processing medium is used repeatedly for processing successive elements it may comprise after some time a minor amount of hydroquinone, which has diffused from the element into the processing medium.
• a hydrophilic colloid intermediate layer e.g., a gelatin layer is arranged between the support and the light-sensitive silver halide emulsion layer of the lithmaterial.
• Such hydrophilic colloid intermediate layer has a weight preferably comprised between about 2 and about g of hydrophilic colloid, more particularly gelatin, per sq.m.
• hydroquinone is preferably incorporated in .such hydrophilic colloid layerarranged between the support and the emulsion layer and/or in a hydrophilic colloid layer coated over the emulsion layer, e. g., a gelatin protective surface coating.
• the hydroquinone developing agent is incorporated into the lith-mate'rialin anamount preferably comprised between about 5 and about mmol per sq.m.
• the hydroxylamine compounds may be used in widely varying amounts. Dependent on the particular compound involved they are used preferably in an amount comprised between about 0.5 g and about 50 g per litre of alkaline development activator. When used in the photographic element itself they are preferably used in amounts between about 50 mg and about 1 g per sq.m.
• the silver halides are dispersed in hydrophilic colloid materials used as binders which include gelatin, collodion, gum arabic, casein, zein, cellulose ester derivatives such as alkyl esters of carboxylated cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, alginic acid, polyvinyl alcohol and other synthetic resins well known in the art.
• Gelatin is preferably used as hydrophilic colloid binder.
• the binding agents for the emulsion layer may also contain dispersed polymerized vinyl compounds. Such compounds are disclosed e.g., in the US. Pat. Nos. 3,142,568 of Robert William Nottorf issued July 28, 1964, 3,193,386 of Clayton F. A.
• Silver halide emulsions wherein the binding agent contains a dispersed polymerised vinyl compound provide particularly good results in eliminating drag streaks and dot distortions.
• Thev silver halide emulsions may be chemically sensitized by effecting the ripening in the presence of 'small amounts of sulphur-containing compounds such as allyl thiocyanate, ally] thiourea, sodium thiosulphate, etc.
• the emulsions may also be sensitized by means of reductors for instance tin compounds as described in United Kingdom Patent Specification No. 789,823 filed Apr. 29, 1955 by Gevaert Photo-Producten NV. and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium compounds.
• the emulsions may be used without being spectrally sensitized; however, it is advantageous to spectrally sensitize them according to methods well known in the art to make them ortho-sensitized or panchromatically sensitized.
• Spectral sensitizers that can be used are e.g., the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryl dyes, oxonol dyes and the like.
• Such like spectrally sensitizing dyes have been described by F. M. Hamer in The Cyanine dyes and relates compounds (1964).
• the silver halide emulsion layer and/or other hydrophilic colloid layers of the high-contrast photographic elements can also contain conventional addenda for example, plasticizers, coating aids, antistaining agents, fog-inhibiting compounds and emulsion stabilizers e.g., the azaindenes, such as 5-methyl-7-hydroxy-s-triazolo[1,5- a]pyrimidine, and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium hydrogen sulphite), maleic dialdehyde, aziridines, dioxan derivatives, and oxypolysac charides, as well as hardening agent precursor compounds which set free the effective hardener only in alkaline medium.
• plasticizers e.g., plasticizers, coating aids, antistaining agents, fog-inhibiting compounds and emulsion stabilizers
• polyoxyalkylene compounds which may be present either in the lith-material or in the development activator or in both.
• polyoxyalkylene compounds are widely known for use in lith-materials and/or lith developers and include any polymeric compound comprising a polyalkylene oxide chain e.g., polyethylene glycol, preferably having a molecular weight of 1500 or more and other ethylene oxide compounds as described amongst others in the United Kingdom Patent Specification Nos. 600,058 filed Jan. 10, 1946 by E. I. du Pont de Nemours, 871,801 filed Nov. 30, 1956 by Kodak Ltd., 920,637 filed May 7, 1959, 940,051 filed Nov.
• the polyethylene oxide compounds may be present in the development activator in an amount ranging from about 0.1 g to about 1 g per litre.
• the lith-material either in the silver. halide emulsion layer or an adjacent water-permeable insensitive layer they are preferably used in amounts ranging from about 0.010 g to about 1 g per mole of silver halide.
• N-vinyl-Z-pyrrolidone polymer or copolymer including addition complexes thereof with iodine as described in British Pat. No. 1,197,306 filed Sept. 19, 1966 by Agfa-Gevaert N.V.
• N-vinyl-2- pyrrolidone polymers or copolymers may be used in the silver halide emulsion layer or in another hydrophilic colloid layer in water-permeable relationship with the emulsion layer as well as in the alkaline development activator.
• onium or polyonium compounds preferably of the ammonium, phosphonium and sulphonium type or mixtures thereof.
• onium compounds are e.g., dodecyl-trimethylammonium ptoluene sulphonate, nonyl pyridinium perchlorate,
• polyoxyalkylenes e.g., polyoxyalkylene bispyridinium salts for example 1,1 '-[ethylenetris(oxyethylene) ]bis( pyridinium-p-tolusulphonate) etc.
• onium compounds can be found in U.S. Pat. Nos. 2,271,622 of BurtH. Carroll and Charles F. H. Allen issued Feb. 3, 1942, 2,271,623 of Burt H. Carroll issued Feb. 3, 1942, 2,275,727 of Burt H. Carroll and Charles F. H. Allen issued Mar. 10, 1942, 2,288,226 of Burt 11. Carroll and. Charles F. H. Allen issued June 30, 1942, 2,944,898 of Dorothy J. Beavers, Charles V. Wilson and James L.
• the silver halide lith-emulsions of use according to the invention may be coated on a wide variety of sup-, ports.
• Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethy1ene terephthalate) film, and related films of resinous materials, as well as glass, paper, metal and the like.
• Supports such as paper, which are coated with a-olefin polymers, particularly polymers of a-olefins containing two or more carbon atoms, as exemplified by polyethylene polypropylene, ethylene-butylene copolymers and the like can also be employed.
• the lith-material may comprise all conventional layers used in silver halide elements e.g., subbing layers, filter layers, U.V.-absorbing layers, antistatic layers, protective surface coatings, etc.
• the alkaline composition for effecting development of the exposed lith-material may comprise all kinds of ingredients as commonly employed in lith-type developers, for example thickening agents e.g., carboxymethylcellulose, compounds releasing halide ions e.g., potassium bromide, polyoxyalkylene compounds, N-vinyl-2-pyrrolidone polymers and copolymers, and onium compounds as referred to above, preservatives e.g., potassium metabisulphite, sodium formaldehyde hydrogen sulphite, and triethanolamine sulphite, watersoftening agents e.g., polyphosphates and derivatives of ethylenediamine, tetraacetic acid, wetting agents, etc.
• thickening agents e.g., carboxymethylcellulose
• compounds releasing halide ions e.g., potassium bromide, polyoxyalkylene compounds, N-vinyl-2-pyrrolidone polymers and copolymers
• onium compounds as
• Preservatives for developing agents may also be incorporated into the hydroquinone-containing lith material.
• the processing solution may comprise low as well as high sulphite content since the hydroquinone developing agent is present in the silver halide element.
• the pH of the alkaline processing solution is generally at least about pH 9, preferably at least about pH 1 1.
• the developed material may be fixed in the usual way e.g., by means of a water-soluble thiosulphate and then washed, or it may be treated with a stabilizing solution comprising an agent capable of converting non-exposed'silver halide in substantially lightinsensitive complexes, which need not be removed by washing, e.g., potassium and ammonium thiocyanate.
• a stabilizing solution comprising an agent capable of converting non-exposed'silver halide in substantially lightinsensitive complexes, which need not be removed by washing, e.g., potassium and ammonium thiocyanate.
• the developed material may be treated with a stabilizing and a fixing solution as described in U.S. Pat. No. 3,637,389 of Emiel A. Hofman issued Jan. 25, 1972.
• Processing of the exposed photographic element can occur in an automatic apparatus wherein the exposed material is transported at a substantially constant speed through the processing stations.
• the exposure station may be coupled to the processing stations of the automatic apparatus.
• a polyethylene terephthalate support was provided with a gelatin layer comprising hydroquinone in a ratio of 8 g of gelatin and 1.77 g of hydroquinone per sq.m.
• the gelatin layer was overcoated with a gelatino silver chlorobromoiodide emulsion (88.7 mole percent of chloride, 1 1 mole percent of bromide and 0.3 mole percent ofiodide) in such a way that per sq.m. an amount of silver halide corresponding to 6 g of silver nitrate waspresent.
• the silver halide emulsion layer was then overcoated with a gelatin antistress layer in a ratio of 0.3 g of gelatin per sq.m.
• the light-sensitive material formed was divided into several aliquot strips. Under identical circumstances each strip was exposed through a step wedge with constant 0.15 and treated at 25C for increasing times in one of the following development activating compositions A, B and C:
• COMPOSITION A anhydrous sodium carbonate potassium bromide l g water to make 1 sodium hydroxide to adjust pH to 12
• COMPOSlTlON B Same as A but comprising in addition g of hydroxylamine sulphate.
• COMPOSlTlON C Same as A but comprising in addition g of hydroxylamine sulphate.
• gradient in toe is meant the average gradient measured between density 0.1 and 1 above fog.
• EXAMPLE 2 A photographic material was prepared as described in example 1 and divided into several aliquot strips. Under identical circumstances, the strips were exposed through a step wedge with constant 0.15 and treated at 25C for increasing times in a development activating solution of the following composition:
• anhydrous sodium carbonate I00 g sodium hydroxide 5 g 100 g triethanolamine sulphite 10 ml polyethylene glycol (molecular weight litre 4000) l g potassium bromide 0.6 g l, l '-[ethylene-tris(oxyethylene )]bis (pyridinium p-tolusulphonate) 100 mg water to make 1 litre (pH ll) to which one of the hydroxylamine compounds listed in the table below was added in the amount given.
• the dot quality was evaluated in shadow (10 percent black dot coverage middle (50 percent black dot coverage) and highlight percent black dot coverage) tone areas and given a quality from 0, which is excellent to 4 which is extremely poor. Any dot quality above 3 is generally not acceptable.
• Method of producing high-contrast images by exposure and development of a photographic lith-type sil-' ver halide material comprising a support and a silver halide emulsion layer containing at least about 50 mole percent of silver chloride, at least about 5 mole percent of silver bromide and from 0 to about 5 mole percent of silver iodide, wherein the said'photographic lith-type material incorporates hydroquinone as developing agent, and development is effected by treatment of the exposed material with an alkaline development activator in the presence of hydroxylamine or a salt thereof or of a N-monosubstituted hydroxylamine or a salt thereof.
• R is hydrogen, an alkyl group or an aryl group.
• Method according to claim 1 wherein the lithmaterial and/or the alkaline development activator comprises a polyoxyethylene compound.
• Method according to claim 1, wherein the lithmaterial and/or the alkaline development activator comprises a N-vinyl-2-pyrrolidone polymer or copolymer.
• Method according to claim 13 wherein after development the material is fixed and washed.
• a photographic lith-type silver halide material comprising a support and a silver halide emulsion layer containing at least about 50 mole percent of silver chloride, at least about 5 mole percent of silver bromide and from to about m olepercent of silver iodide,
• said material incorporates hydroquinone and hydroxylamine or a salt thereof or a N-monosubstituted hydroxylamine or a salt thereof.
• R is hydrogen, an alkyl group or an aryl group.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (5)

• 1972
  • 1972-05-26 GB GB2506872A patent/GB1417712A/en not_active Expired
• 1973
  • 1973-05-02 FR FR7315796A patent/FR2189770B1/fr not_active Expired
  • 1973-05-10 IT IT86228/73A patent/IT1000421B/it active
  • 1973-05-12 DE DE2324161A patent/DE2324161A1/de not_active Withdrawn
  • 1973-05-17 BE BE1005055A patent/BE799642A/nl unknown
  • 1973-05-17 CH CH696173A patent/CH580828A5/xx not_active IP Right Cessation
  • 1973-05-18 US US00361576A patent/US3847618A/en not_active Expired - Lifetime
  • 1973-05-18 CA CA171,811A patent/CA1000993A/en not_active Expired
  • 1973-05-18 SU SU7301921302A patent/SU576977A3/ru active
  • 1973-05-22 NL NL7307125A patent/NL7307125A/xx unknown
  • 1973-05-24 JP JP5819073A patent/JPS5630848B2/ja not_active Expired

Patent Citations (5)

Non-Patent Citations (1)

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