EP0992845A1 - Lichtempfindliches Silberhalogenidmaterial mit verbesserten Oberflächeneigenschaften nach Behandlung - Google Patents

Lichtempfindliches Silberhalogenidmaterial mit verbesserten Oberflächeneigenschaften nach Behandlung Download PDF

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Publication number
EP0992845A1
EP0992845A1 EP99203063A EP99203063A EP0992845A1 EP 0992845 A1 EP0992845 A1 EP 0992845A1 EP 99203063 A EP99203063 A EP 99203063A EP 99203063 A EP99203063 A EP 99203063A EP 0992845 A1 EP0992845 A1 EP 0992845A1
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EP
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Prior art keywords
latex
gelatin
afterlayer
layer
silver halide
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EP99203063A
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English (en)
French (fr)
Inventor
Marc c/o Agfa-Gevaert N.V. Van den Zegel
Hubert C/O Agfa-Gevaert N.V. Vandenabeele
Eddy c/o Agfa-Gevaert N.V. Michiels
Frank c/o Agfa-Gevaert N.V. Louwet
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP99203063A priority Critical patent/EP0992845A1/de
Publication of EP0992845A1 publication Critical patent/EP0992845A1/de
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    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
    • 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
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes

Definitions

  • the invention is related to a light-sensitive silver halide photographic material having satisfactory developability, reduced pressure sensitivity and excellent surface characteristics after processing in both hardener containing and hardener free processing.
  • EP-A 0 806 705 wherein a method has been disclosed of processing an image-wise exposed light-sensitive silver halide material by the steps of developing, fixing in a fixer solution containing less than 4 g per litre of aluminum ions expressed as an equivalent amount of aluminum sulphate, rinsing and drying; characterized in that said material comprises a support and on one or both sides thereof at least one light-sensitive silver halide emulsion layer and a gelatinous protective antistress layer, wherein said antistress layer comprises at least one polymer latex in such an amount that there is a ratio by weight of latex to gelatin is from 0.5 to 1.5 and wherein said material is hardened to such an extent that its swelling degree after immersing said material for 3 minutes in demineral
  • a light-sensitive silver halide photographic material comprising a support and on one or both sides thereof at least one light-sensitive silver halide emulsion layer, a gelatinous protective antistress layer and, adjacent thereto as an outermost layer, a gelatinous afterlayer characterized in that said afterlayer comprises at least one polymer latex, being a polybutylacrylate, a polybutylmethacrylate latex or a polyurethane latex, or a copolymer latex being a copolymer poly(butyl methacrylate) polyacrylamide N-substituted sulfo-isobutyl salt, in a ratio amount by weight of (co)polymer latex to gelatin from 0.2:1 up to 5:1 and a total amount of (co)polymer latex and gelatin of at least 0.10 g/m 2 .
  • Preferred (co)polymer latices used in the protective antistress layer and/or outermost afterlayer of the light-sensitive silver halide material according to the present invention are cross-linked polymers and can be prepared as described e.g. in US-A 4,301,240 by emulsion polymerisation of aliphatic esters of acrylic and/or methacrylic acid in water in the presence of polyfunctional crosslinking monomers and an emulsifier, followed by saponification of the obtained copolymer.
  • emulsion polymerisation copolymers with a molecular weight well above 500,000 are obtained and the average particle size of the latex is smaller than 150 nm.
  • Another example of the synthesis of ionic cross-linked copolymers can further be found e.g. in EP-A 0 452 568 and the corresponding US-A 5,472,832.
  • a particularly preferred latex of an ionic copolymer for use in the gelatinous protective antistress layer of a light-sensitive silver halide material is a copolymer of butyl methacrylate and acrylamide-N-isobutylsulphonic acid sodium salt as represented in the formula (I).
  • a ratio amount of butylmethacrylate and and acrylamide-N-isobutyl-sulphonic acid sodium salt is at least 80:20 and more preferably about 95:5.
  • Latex compounds are polybutylacrylate and polybutylmethacrylate as examples of non-ionic polymer latex compounds. It is not excluded to use them in combination, e.g. in a mixture with each other or even with other polymers dispersed as a latex as there are polymethylmethacrylate, polymethylacrylate, polyethylacrylate latex compounds and the like. Average particle sizes of the latex particles are in the range from about 50 nm up to about 115 nm as for the latex copolymer according to the formula (I) given hereinbefore.
  • Another particularly preferred latex is a polyurethane latex, which is preferably in the form of a dispersion of an aliphatic anionic polyurethane.
  • IMPRANIL 43056 trademarked product from BAYER AG, Leverkusen, Federal Republic of Germany is very suitable.
  • This IMPRANIL-latex is a 40 % aqueous dispersion of polyurethane prepared from DESMODUR W (trademarked product from BAYER AG), which is a dicyclohexylmethane diisocyanate, and a polyester having a low molecular weight of about 800.
  • the average particle size of the latex may vary between 0.02 and 0.2 ⁇ m.
  • the polyurethane is added to the coating solution as an aqueous latex dispersion.
  • An especially useful polyurethane is the one having a highchual amount of urethane groups, in order to get a high degree of cross-linking and as a consequence low tendency to sticking.
  • a lubricant in an outermost afterlayer on top of the protective antistress layer comprising said polyurethane dispersion may be favourable.
  • Said polyurethane latex can moreover be loaded with e.g. a developing agent by addition of the aqueous loadable polyurethane latex to a solution of useful agent(s) as e.g. a developing agent in a water-miscible organic solvent e.g.
  • a mixture of developing agents including a dihydroxybenzene like hydroquinone and a 3-pyrazolidine-1-one developing agent as e.g. 1-phenyl-3-pyrazolidine-1-one also known as "phenidone", being an electron transfer agent or super additive developer, can be used in combination, in that case preferably in a respective molar ratio of from 2/1 to 10/1.
  • dihydroxybenzene or dihydroxybenzenes is(are) preferably present in an amount of from 0.05 to 0.5 g for a coverage of silver halide equivalent with 1 g of silver nitrate.
  • Ascorbic acid iso-ascorbic acid whether or not in combination with the preferred developing agent(s) can also be used.
  • activation material can be obtained which can be developed by means of an alkaline solution.
  • the material according to the present invention when comprising a polyurethane as polymer latex, said latex is an aliphatic anionic polyurethane.
  • one or more latex (co)polymer(s) is(are) optionally present in the gelatinous protective antistress layer as the objects of the present invention are also fulfilled when said protective antistress layer is free from any polymer latex. It is however required for the latex (co)polymer(s) to be at least present in the outermost gelatinous afterlayer of the material according to the present invention: at least one (co)polymer latex in a ratio amount by weight of (co)polymer latex to gelatin from 0.2:1 up to 5:1, and more preferably in a ratio of from 0.3:1 up to 3:1, and a total amount of (co)polymer latex and gelatin of at least 0.10 g/m 2 is required.
  • said material has a total amount of (co)polymer latex and gelatin of up to 1.2 g/m 2 in said outermost gelatinous afterlayer, which is in favour of better spreading of water in the rinsing step (and even drying properties or absence of "water spot defects") and in favour of pressure sensitivity.
  • a total amount of (co)polymer latex and gelatin of up to 1.2 g/m 2 in said outermost gelatinous afterlayer, which is in favour of better spreading of water in the rinsing step (and even drying properties or absence of "water spot defects") and in favour of pressure sensitivity.
  • Preferred amounts of gelatin in said outermost afterlayer are in the range from 0.10-0.40 g/m 2
  • preferred amounts of latex (co)polymer(s) are in the range from 0.05-0.60 g/m 2 and more preferably in the range from 0.10-0.40 g/m 2 .
  • the material according to the present invention is coated with an amount of gelatin as a binder material (known as gelatin coverage) in the protective antistress coating of not more than than 1.5 g per m 2 and more preferably in the range of from 0.20 to 1.0 g per m 2 and in the outermost afterlayer the gelatin coverage is in the range of from 0.05 to 0.50 g per m 2 , more preferably from 0.10 to 0.40 g per m 2 and still more preferably from 0.20 to 0.40 g per m 2 .
  • gelatin coverage an amount of gelatin as a binder material in the protective antistress coating of not more than than 1.5 g per m 2 and more preferably in the range of from 0.20 to 1.0 g per m 2 and in the outermost afterlayer the gelatin coverage is in the range of from 0.05 to 0.50 g per m 2 , more preferably from 0.10 to 0.40 g per m 2 and still more preferably from 0.20 to 0.40 g per m 2 .
  • the material according to the present invention is also intended to be processable in a developer and a fixer without hardeners (like the environmental unfriendly glutaraldehyd)
  • the material of the present invention is hardened to such an extent that its swelling degree after immersing said material for 3 minutes in demineralized water of 25 °C is not more than 300 %, and even more preferably less than 200 %.
  • said swelling degree should not be higher.
  • the said latex-type (co)polymers may further optionally be present in one or more emulsion layer(s) coated between the protective antistress layer and a subbed support, the subbing layer of which may be overcoated with at least one gelatinous intermediate layer.
  • Layers and layer arrangements which can be applied to the film material, apart from the requirement to have an afterlayer, coated adjacent and as an outermost layer of the material of the present invention are those described in US-A's 4,092,168; 4,311,787 and 5,693,370 and in EP-A 's 0 712 034; 0 712 036; 0 677 773; 0 678 772; 0 610 608; 0 610 609 and 0 569 075, in DE- A 2,453,217 and in GB-A 7,907,440.
  • hydrophilic colloid binders differing from gelatin that can be homogeneously mixed therewith may be present and are e.g. other proteinaceous colloids, polysaccharides as e.g. starch and polydextranes, as well as synthetic substitutes for gelatin as e.g.
  • poly-N-vinylpyrrolidone polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyamethyl-acrylate, polyethyl-acrylate, polymethyl-methacrylate, polyethyl-methacrylate, polyvinyl imidazole, polyvinyl pyrazole and derivatives thereof as well as styrene-male ⁇ c acid or a styrene-male ⁇ c acid anhydrid type copolymer.
  • non-ionic surfactants such as saponins, alkylene oxides e.g.
  • polyethylene glycol polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy-, sulpho-, phospho-, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic
  • Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
  • gelatin Conventional lime-treated or acid treated gelatin can be used. The preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, p. 295 and next pages.
  • the gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N° 16, p.30 (1966).
  • said gelatin can be replaced in part or integrally by synthetic polymers as cited hereinbefore or by natural or semi-synthetic polymers.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • Semi-synthetic substitutes for gelatin are modified natural products as e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerisable monomers on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
  • gelatin in the antistress layer is partially replaced by colloidal silica as it gives rise to a further improvement of the obtained properties of the material according to the present invention.
  • colloidal silica having an average particle size of not larger than 10 nm and having a surface area of at least 300 m 2 per gram is used.
  • Especially preferred colloidal silica particles have a surface area of 500 m 2 per gram and an average grain size smaller than 7 nm.
  • Such type of silica is sold under the name KIESELSOL 500 (KIESELSOL is a registered trade name of Bayer AG, Leverkusen, West-Germany).
  • Colloidal silica is preferably present at a coverage of at least 50 mg per m 2 . Further the coverage of said colloidal silica in the anti-stress layer is preferably in the range of 50 mg to 500 mg per m 2 .
  • the antistress layer may further contain friction-lowering substance(s) such as dispersed wax particles (carnaubawax or montanwax) or polyethylene particles, fluorinated polymer particles, silicon polymer particles etc., in order to further reduce the sticking tendency of the layer especially in an atmosphere of high relative humidity.
  • friction-lowering substance(s) such as dispersed wax particles (carnaubawax or montanwax) or polyethylene particles, fluorinated polymer particles, silicon polymer particles etc.
  • the gelatin binder can be forehardened with appropriate hardening agents such as those of the epoxide type, those of the ethylene-mine type, those of the vinylsulfone type as e.g. 1,3-vinylsulphonyl-2-propanol, bis-vinyl-sulphonyl methyl or bis-vinyl sulphonyl ethyl ether, hydroxy substituted vinyl sulphonyl hardeners, chromium salts as e.g. chromium acetate and chromium alum, aldehydes as e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds as e.g.
  • dimethylolurea and methyloldimethylhydantoin dioxan derivatives as e.g. 2,3-dihydroxy-dioxan, active vinyl compounds as e.g. 1,3, 5-triacryloyl-hexahydro-s-triazine, active halogen compounds as e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids as e.g. mucochloric acid and mucophenoxychloric acid.
  • These hardeners can be used alone or in combination.
  • the binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US-A 4,063,952 and with the onium compounds disclosed in EP-A 0 408 143.
  • non-ionic surfactant(s) having antistatic characteristics such as e.g. polyoxyethylene compounds.
  • the said surfactant(s) is(are) present in an optionally present outermost layer.
  • Said layer may be a gelatin free afterlayer or a thin gelatinous layer.
  • a latex (co)polymer having antistatic properties is added to the protective antistress layer containing the latex (co)polymer(s) set forth hereinbefore. Said latex (co)polymer is present in an amount of up to 0.5 g/m 2 per side.
  • a preferred one is the latex of a cross-linked polymer, being a copolymer of an acrylic and/or methacrylic acid ester including 90-99 mole % of acrylate and/or methacrylate units and 1 to 10 mole % of tetraallyloxyethane units as polyfunctional crosslinking monomer, wherein in said copolymer at least 75 % of the ester groups have been transformed into alkali metal carboxylate groups, thus exhibiting ionic characteristics: especially preferred as a cross-linked ionic polymer is poly( [c.l.] tetraallyloxyethane-co-methyl acrylate/acrylic acid), the formula (II) of which is given hereinafter with a preferable 3/18/79 molar ratio.
  • the afterlayer may further comprise spacing agents and coating aids such as wetting agents as e.g. perfluorinated surfactants.
  • Spacing agents which may also be present in the protective antistress layer in generally have an average particle size which is comprised between 0.2 and 10 ⁇ m. Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath.
  • Suitable spacing agents can be made i.a. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-A 4,614,708.
  • the coating of the layers of the material of the present invention may proceed by any coating technique known in the art, as e.g. by doctor blade coating, air knife coating, curtain coating, slide hopper coating or meniscus coating, which are coating techniques known from the production of photographic silver emulsion layer materials.
  • Preferred thickening agents include aqueous polymers such as polystyrene sulphonic acid, sulphuric acid esters, polysaccharides, polymers having a sulphonic acid group, a carboxylic acid group or a phosphoric acid group, polyacrylamide, polymethacrylic acid or its salt, copolymers from acrylamide and methacrylic acid and salts derived thereof, copolymers from 2-acrylamido-2-methyl-propane sulphonic acid, polyvinyl alcohol, alginate, xanthane, carraghenan, synthetic (smectite) clays and the like.
  • aqueous polymers such as polystyrene sulphonic acid, sulphuric acid esters, polysaccharides, polymers having a sulphonic acid group, a carboxylic acid group or a phosphoric acid group, polyacrylamide, polymethacrylic acid or its salt, copolymers from acrylamide and meth
  • Polymeric thickeners well-known from the literature resulting in thickening of the coating solution may be used independently or in combination.
  • Patents concerning thickening agents are e.g. US-A 3,167,410, Belgian Patent No. 558,143, JP-A's 53/18687 and 58/36768 and DE-A 3 836 945.
  • the silver halide photographic material may contain in the light-sensitive emulsion layer(s) and/or in one or more layers in water-permeable relationship with said silver halide emulsion layer(s) any of the kinds of compounds customarily used in such layers for improving the photographic process, manufacture or preservability (storage).
  • such layers may incorporate one or more coating aids, stabilising agents or antifogging agents as described e.g. in GB-A 1,007,020 filed March 6, 1963 by Agfa A.G., plasticizers, development-modifying agents e.g.
  • thioethers acting as silver chelating agents with at least two sulphur atoms as donors are used.
  • a survey of thioether compounds suitable for incorporation in silver halide emulsion layers of widely varying silver halide composition has been given in the EP-A 0 026 520. Useful compounds have further been described in EP-A's 0 634 688 and 0 674 215.
  • Silver halide emulsion crystals used in the silver halide emulsion layer(s) of the material of the present invention are composed of silver chloride, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, silver bromide or silver bromoiodide. Regular as well as tabular crystals may be present, as well as mixtures thereof. Crystals having a different crystal habit may be coated in different layers as e.g. in EP-A 0 770 909.
  • silver halide crystals having a regular crystal habit preferably have an average grain size of at least 0.15 ⁇ m, up to at most 1.2 ⁇ m, more preferably up to 1.0 ⁇ m and still more preferably up to 0.8 ⁇ m.
  • Silver halide crystals having tabular ⁇ 111 ⁇ major faces accounting for at least 50 % of the total projected area preferably have an average diameter from 0.5 to 2.5 ⁇ m and an average thickness from 0.06 to at most 0.3 ⁇ m, and even more preferred to at most 0.2 ⁇ m.
  • Said silver halide crystals may have been prepared in gelatin and/or in colloidal silica as a protective colloid. Preparations in colloidal silica have e.g. been described, in EP-A's 0 677 773; 0 682 287; 0 649 051 and 0 754 964.
  • Supports and subbing layers coated adjacent thereto can be those as described in RD 36544 (published September 1994), chapter XV, polyethylene naphthalate inclusive.
  • the hydrophobic resin support may be provided with one or more subbing layers known to those skilled in the art for adhering thereto a hydrophilic colloid layer.
  • Suitable subbing layers for polyethylene terephthalate supports are described e.g. in US-A's 3,397,988, 3,649,336, 4,123,278 and 4,478,907.
  • a useful subbing layer is disclosed e.g. in JP-A 01 166 031.
  • Vinylidene chloride and styrene-butadiene copolymers are the most well-known polymers for practical use as subbing layer ingredients in the material to be processed according to the method of the present invention.
  • Photographic silver halide emulsion materials suitable for use in the processing method of this invention are materials for continuous tone or halftone photography, microphotography and radiography, in black-and-white as well as colour photographic materials. Said materials are thus selected from the group consisting of materials having one or more light-sensitive silver halide emulsion layers at one or at both sides of the support.
  • preferred materials are X-ray materials, single-side as well as double side coated, and more preferred medical X-ray materials.
  • Said materials may be imagewise exposed by means of any radiation source, depending on their application as has been described e.g. in RD 36544, chapter XVI.
  • Ecological advantages of the processing method of said imagewise exposed materials according to the present invention are related with the use of fixer solutions ready-for-use containing less than 4 g of aluminum per litre expressed as an equivalent amount of aluminum sulphate.
  • a time saving factor is the total processing time: rapid processing proceeds within a time of less than 90 seconds, more preferred within a time of less than 50 seconds e.g. within a time from 20 to 45 seconds, in automatic processing machines as e.g. CURIX HT 530, trade marketed product from Agfa-Gevaert N.V..
  • fixers having high sodium thiosulphate concentrations are preferred over fixers containing ammonium thiosulphate. They are useful in those circumstances wherein no replenishment system is available or where it is desirable to minimize the replenishment amounts. Such fixers retain a high silver binding capacity and a sufficient fixing speed even after prolonged continuous processing without replenishment or with minimum replenishment. An example thereof has been given in Research Disclosure 355 039, p. 736-737, published November 1, 1993.
  • fixation proceeds in a fixer at a pH value of at least 4.6 and even more preferred in a fixer having a pH value of at least 5.0, a condition which can be better fulfilled the lower the concentration of aluminum ions is as precipitation of aluminum hydroxyde should be avoided.
  • no aluminum is present at all as has already been established hereinbefore.
  • drying preferably proceeds by means of infrared drying means as has e.g. been described in EP-A 0 620 482 for non-destructive testing film materials.
  • infrared drying means as has e.g. been described in EP-A 0 620 482 for non-destructive testing film materials.
  • improvement of surface characteristics is in the best mode, especially thanks to the composition of the antistress layer.
  • a material according to the present invention offers, after rapid processing in hardener free developers and fixers as well as in hardener containing developers and fixers (wherein fixing preferably proceeds in the presence of low amounts of aluminum, preferably less than 4 g per liter of aluminum ions expressed as an equivalent amount of aluminum sulphate, having a pH value of at least 4.6 in order to avoid odour or smell), the desired properties, being absence of or significant reduction of water spot defects without loss of developability as can be concluded from sensitometric properties (especially speed and contrast) in rapid processing conditions (45 ⁇ processing, in automatic processing machines as well as in manual processing). In case of hardener free processing an excellent glare or gloss level is retained after said processing, again without loss in developability.
  • a photographic material was prepared composed of
  • reaction vessel 28 ml of solutions 1 and 2 were introduced into a reaction vessel in 28 seconds using the double jet technique.
  • Said reaction vessel initially contained 2.127 liter of destilled water at 45°C, 10.6 grams of potassium bromide and 6 grams of inert gelatin and was held at 55°C. After one minute the reaction temperature of this mixture was raised to 70°C in 20 minutes and 47.5 grams of phthalated gelatin in 475 ml destilled water were added. After 10 minutes the neutralization step was started.
  • a double jet precipitation was started using solutions 1 and 2: during 1 minute solution 1 was added at a flow rate of 7.5 ml per minute, while solution 2 was added at a rate of 7.7 ml/min., meanwhile maintaining the UAg value at + 10 mV.
  • the double jet precipitation continued for 31 min. 30 seconds at a flow rate while increasing the rate of solution 1 up to 22.2 ml per minute and solution 2 up to 22.6 ml per minute, meanwhile maintaining the UAg value at + 10 mV again.
  • solution 1 was injected in the reaction vessel at a flow rate of 7.5 ml per minute, while solution 3 was injected at the same flow rate.
  • the flow rates were increased during 41 minutes and 50 seconds up to 37.5 ml per minute, meanwhile maintaining a UAg value in the reaction vessel of + 100 mV.
  • the stirring velocity was decreased from 550 to 250 rpm.
  • the tabular grains of the emulsion thus obtained had the following characteristics, measured with electron microscopic techniques:
  • the dispersed emulsion was optimally sulphur and gold sensitized in the presence of sodium thiocyanate and anhydro-5,5'-dichloro-3,3'-bis(n. sulfobutyl)-9-ethyloxacarbocyanine hydroxide.
  • reaction vessel 16.3 ml of solutions 1 and 2 were introduced into a reaction vessel in 35 seconds using the double jet technique.
  • Said reaction vessel initially contained 2.127 liter of destilled water at 45°C, 10.6 grams of potassium bromide and 6 grams of inert gelatin and was held at 55°C. After one minute the reaction temperature of this mixture was raised to 70°C in 20 minutes and 47.5 grams of phthalated gelatin in 475 ml destilled water were added.
  • the stirring velocity in the reaction vessel was held at 150 rpm. Before the first growth step the stirring velocity was increased up to 400 rpm.
  • a double jet precipitation was started using solutions 1 and 2: during 1 minute solution 1 was added at a flow rate of 7.5 ml per minute, while solution 2 was added at a rate of 7.9 ml/min., meanwhile maintaining the UAg value (potential versus silver/silver chloride reference electrode) at - 15 mV.
  • the double jet precipitation continued for 35 min. 38 seconds at a flow rate while increasing the rate of solution 1 up to 14.4 ml per minute and solution 2 up to 15.2 ml per minute, meanwhile maintaining the UAg value at - 15 mV again.
  • solution 1 was injected in the reaction vessel at a flow rate of 7.5 ml per minute, while solution 3 was injected at the same flow rate.
  • the flow rates were increased during 59 minutes and 30 seconds up to 22.5 ml per minute, meanwhile maintaining a UAg value in the reaction vessel of + 100 mV.
  • the stirring velocity was thereafter decreased to 250 rpm.
  • the tabular grains of the emulsion thus obtained had the following characteristics, measured with electron microscopic techniques:
  • the pH value was lowered to 3.5 with diluted sulphuric acid and the emulsion was washed using demineralized water of 11°C.
  • demineralized water 11°C.
  • gelatin was added in order to have a gesi (ratio in grams of gelatin to silver) of 0.34 and demineralized water was added in order to have a total weight of 1923 grams.
  • Values of pH and UAg at 40°C were adjusted to 5.5 and + 100 mV.
  • the dispersed emulsion was optimally sulphur and gold sensitized in the presence of sodium thiocyanate and anhydro-5,5'-dichloro-3,3'-bis (n.sulfobutyl) -9-ethyl-oxacarbocyanine hydroxide.
  • Each emulsion was stabilized with 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene. Both emulsions were mixed in order to get a ratio by weight of Emulsion A to Emulsion B of 4:1, gelatin was added and after addition of the normal coating additives the solutions were coated simultaneously together with a protective layer containing a variable amount of gelatin as indicated in Table 1 per m 2 and per side on both sides of a polyethylene terephthalate film support with a thickness of 175 ⁇ m.
  • the said protective antistress layer was coated with the following compounds, expressed in grams per square meter per side: gelatin x 1 g polymethylmethacrylate (average particle diameter : 6 ⁇ m) 0.023 1-p-carboxyphenyl-4, 4'-dimethyl-3-pyrazolidine-1-one 0.054 oleyl-(OCH 2 CH 2 ) 10 OH (absent in the presence of an afterlayer) 0.056 formaldehyd(added just before coating) 0.1 CF 3 -(CF 2 ) 6 -COOH.NH 3 (absent in the presence of an afterlayer) 0.007
  • Polymer latex given in formula (I) hereinbefore was added in variable amounts (y 1 g) as indicated in the same Table I.
  • Polymer latex given in formula (I) hereinbefore was added in variable amounts (y 2 g) as indicated in the Tables where it applies.
  • the resulting photographic material contained per side an amount of silver halide corresponding to 3.89 grams of AgNO 3
  • the processing conditions and the composition of the processing solutions is given hereinafter.
  • the processing of the described photographic materials in accordance with this invention proceeds in the processing machine CURIX HT530TM (Agfa-Gevaert) with following time (in seconds) and temperature (in °C) characteristics: loading 0.2 sec. developing 9.3 sec. 35°C(developer G138®,Agfa-Gevaert NV) cross-over 1.4 sec. rinsing 0.9 sec. cross-over 1.5 sec. fixing 6.6 sec. 35°C (fixer G334®,Agfa-Gevaert NV) cross-over 2.0 sec. rinsing 4.4 sec. 20°C cross-over 4.6 sec. drying 6.7 sec. total 37.6 sec.
  • composition of the hardener-free developer -concentrated part : water 200 ml potassium bromide 12 grams potassium sulphite (65% solution) 249 grams ethylenediaminetetraacetic acid, sodium salt, trihydrate 9.6 grams hydroquinone 106 grams 5-methylbenzotriazole 0.076 grams 1-phenyl-5-mercaptotetrazole 0.040 grams sodiumtetraborate (decahydrate) 70 grams potassium carbonate 38 grams potassium hydroxide 49 grams diethylene glycol 11 grams potassium iodide 0.088 grams 4-hydroxymethyl-4-methyl-1phenyl 3-pyrazolidinone 12 grams Water to make 1 liter pH adjusted to 11.15 at 25°C with potassium hydroxide.
  • composition of the hardener-free fixer -concentrated part : ammonium thiosulfate (78% solution) 661 grams sodium sulphite 54 grams boric acid 25 grams sodium acetate-trihydrate 70 grams acetic acid 40 grams water to make 1 liter pH adjusted with acetic acid to 5.30 at 25°C

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP99203063A 1998-10-08 1999-09-20 Lichtempfindliches Silberhalogenidmaterial mit verbesserten Oberflächeneigenschaften nach Behandlung Withdrawn EP0992845A1 (de)

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EP98203412 1998-10-08
EP98203412 1998-10-08
EP99203063A EP0992845A1 (de) 1998-10-08 1999-09-20 Lichtempfindliches Silberhalogenidmaterial mit verbesserten Oberflächeneigenschaften nach Behandlung

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0307855A2 (de) * 1987-09-18 1989-03-22 EASTMAN KODAK COMPANY (a New Jersey corporation) Polymerteilchen, auf die Gelatine aufgepfropft ist
EP0404091A2 (de) * 1989-06-20 1990-12-27 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidmaterialen
US5061595A (en) * 1990-09-24 1991-10-29 Eastman Kodak Company Contact film for use in graphic arts with two overcoat layers
EP0520393A1 (de) * 1991-06-25 1992-12-30 EASTMAN KODAK COMPANY (a New Jersey corporation) Photographisches Element, enthaltend eine Spannung absorbierende, schützende Schicht
EP0751422A1 (de) * 1995-06-27 1997-01-02 Eastman Kodak Company Photographisches Element mit verbesserter Kratz- und Abriebfestigkeit
EP0886177A1 (de) * 1997-06-19 1998-12-23 Eastman Kodak Company Durch Mikrosuspension Verfahren hergestellte polymerische Partikeln enthaltendes photographisches Element

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0307855A2 (de) * 1987-09-18 1989-03-22 EASTMAN KODAK COMPANY (a New Jersey corporation) Polymerteilchen, auf die Gelatine aufgepfropft ist
EP0404091A2 (de) * 1989-06-20 1990-12-27 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidmaterialen
US5061595A (en) * 1990-09-24 1991-10-29 Eastman Kodak Company Contact film for use in graphic arts with two overcoat layers
EP0520393A1 (de) * 1991-06-25 1992-12-30 EASTMAN KODAK COMPANY (a New Jersey corporation) Photographisches Element, enthaltend eine Spannung absorbierende, schützende Schicht
EP0751422A1 (de) * 1995-06-27 1997-01-02 Eastman Kodak Company Photographisches Element mit verbesserter Kratz- und Abriebfestigkeit
EP0886177A1 (de) * 1997-06-19 1998-12-23 Eastman Kodak Company Durch Mikrosuspension Verfahren hergestellte polymerische Partikeln enthaltendes photographisches Element

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