EP1170631A1 - Matériau photographique d'enregistrement - Google Patents

Matériau photographique d'enregistrement Download PDF

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Publication number
EP1170631A1
EP1170631A1 EP00202410A EP00202410A EP1170631A1 EP 1170631 A1 EP1170631 A1 EP 1170631A1 EP 00202410 A EP00202410 A EP 00202410A EP 00202410 A EP00202410 A EP 00202410A EP 1170631 A1 EP1170631 A1 EP 1170631A1
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EP
European Patent Office
Prior art keywords
layer
gelatin
emulsion
latex
silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00202410A
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German (de)
English (en)
Inventor
Roland c/o Agfa-Gevaert N.V. Claes
Stefaan c/o Agfa-Gevaert N.V. Lingier
Etienne C/O Agfa-Gevaert N.V. Van Thillo
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Agfa NV
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Agfa Gevaert NV
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Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP00202410A priority Critical patent/EP1170631A1/fr
Priority to US09/891,962 priority patent/US6432606B1/en
Priority to JP2001206070A priority patent/JP2002040596A/ja
Publication of EP1170631A1 publication Critical patent/EP1170631A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/93Macromolecular substances therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/74Applying photosensitive compositions to the base; Drying processes therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/795Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
    • G03C1/7954Polyesters
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83Organic dyestuffs therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/74Applying photosensitive compositions to the base; Drying processes therefor
    • G03C2001/7433Curtain coating
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • G03C2001/7628Back layer
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025Silver content
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00Details
    • G03C2200/36Latex

Definitions

  • the present invention relates to an improved photographic recording material for graphic arts prepress.
  • Photosensitive materials based on silver halide chemistry are used in a lot of applications, e.g. photographic materials for general amateur and professional photography in black-and white or colour, recording and printing materials for the motion picture industry, and materials for the recording and duplication of medical diagnostic images. Further specific materials are developed for micrography, non-destructive testing and graphic arts pre-press.
  • graphic arts reproduction processes the original image appearing to have a continuous tone gradation is reproduced in a screening process by a collection of large number of dots, either by optical means in the case of a camera film or by electronic means in case of a recorder film. Apart from camera and recorder films there exist also so-called contact films which are able to duplicate screened images.
  • a photographic recording material for graphic arts comprising a polyester support, subbed on both front and back sides with a latex subbing layer, and further comprising on the front side a gelatin subbing layer, one or more red sensitized emulsion layers having a total silver coverage of at most 3.6 g/m 2 Ag (corresponding to 5.5 g/m 2 , expressed as AgNO 3 ), and a total dry coverage of all other solid ingredients of at most 1.5 g/m 2 , and one or more anti-abrasive layers.
  • the photographic recording material further comprises on the back side an antihalation layer comprising at most 1.5 g/m 2 of gelatin and an antihalation dye.
  • the recording material of the present invention contains one or more emulsion layers, containing silver halide grains, a binder and other solid ingredients. In a most preferred embodiment of this invention there is just one emulsion layer. It is an essential feature of the present invention that the total silver coverage is at most 3.6 g/m 2 Ag (corresponding to 5.5 g/m 2 expressed as AgNO 3 ). It is a further essential feature of the present invention that the total dry coverage of all other solid ingredients is at most 1.5 g/m 2 .
  • Graphic arts recording materials preferably use emulsions containing a majority of chloride, preferably between 50 mole % and 95 mole %, most preferably between 60 mole % and 89 mole %, and a low amount of iodide, the remaining halide being bromide.
  • the photographic emulsion(s) can be prepared from soluble silver salts and soluble halides according to different methods as described e.g. by P. Glafkidès in “Chimie et Physique Photographique”, Paul Montel, Paris (1967), by G.F. Duffin in “Photographic Emulsion Chemistry", The Focal Press, London (1966), and by V.L. Zelikman et al in “Making and Coating Photographic Emulsion", The Focal Press, London (1966). They can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition.
  • the silver halide can be precipitated according to the single-jet method, the double-jet method, the conversion method or an alternation of these different methods.
  • the silver halide emulsions can be doped with various metal salts or complexes such as Rhodium and Iridium dopants.
  • the emulsion can be desalted in the usual ways e.g. by dialysis, by flocculation and re-dispersing, or by ultrafiltration.
  • the light-sensitive silver halide emulsions are preferably chemically sensitized as described e.g. in the above-mentioned "Chimie et Physique Photographique” by P. Glafkidès, in the above-mentioned “Photographic Emulsion Chemistry” by G.F. Duffin, in the above-mentioned “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen Sawe mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines.
  • the emulsions can be sensitized also by means of gold-sulphur ripeners, gold-selenium ripeners or by means of reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, T1, Pd, Pt, or Au.
  • One of these chemical sensitization methods or a combination thereof can be used.
  • the light-sensitive silver halide emulsions can be red sensitized with proper dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
  • Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • Specific patents on red sensitizers include US 4,717,650, FR 2 058 405 and EP 427892.
  • the silver halide emulsion(s) for use in accordance with the present invention may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements or during the photographic treatment thereof.
  • Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion. Suitable examples are disclosed in Research Disclosure Item 36544, September 1994, Chapter VII.
  • the binder is a hydrophilic colloid, preferably gelatin.
  • Gelatin can, however, be replaced in part or integrally by synthetic, semi-synthetic, or natural polymers.
  • the binders of the photographic element can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g.1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g.1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and
  • the emulsion layer further contains a polymeric latex functioning as plasticizer.
  • a preferred latex is copoly(AMPS-butylmethacrylate), wherein AMPS means 2-acrylamido-2-methylpropane sulphonic acid, sodium salt, a monomer from Lubrizol Co..
  • the latex is present in an amount of at least 15 % by weight of all solids the silver halide grains excluded.
  • the photographic emulsion layer may further comprise various kinds of surface-active agents and lubricants in the photographic emulsion layer or in another hydrophilic colloid layer. Suitable surface-active agents and lubricants are disclosed in Research Disclosure Item 36544, September 1994, Chapter IX.
  • the anti-abrasive layer closest to the support contains a mixture of gelatin and a latex. In a most preferred embodiment this layer contains about 0.5 g/m 2 of gelatin and about 0.5 g/m 2 of latex.
  • the latex used may be the same as the latex optionally present in the emulsion layer.
  • the top anti-abrasive layer is a gelatinous layer preferably without latex. Preferably its gelatin coverage is also about 0.5 g/m 2 .
  • the anti-abrasive layer may further contain spacing agents, wetting agents and lubricants, e.g. polyethylene dispersion.
  • polyester support of the recorder film of the present invention is subbed on both sides with a so-called latex subbing layer.
  • An essential ingredient of this latex subbing layer is an adhesion promoting latex.
  • a preferred class of latex polymers for this purpose are vinylidene chloride-containing copolymers having carboxyl functional groups.
  • Illustrative of such polymers are (1) copolymers of vinylidene chloride and an unsaturated carboxylic acid such as acrylic or methacrylic acid, (2) copolymers of vinylidene chloride and a half ester of an unsaturated carboxylic acid such as the monomethylester of itaconic acid, (3) terpolymers of vinylidene chloride, itaconic acid and an alkyl acrylate or methacrylate such as ethyl acrylate or methyl methacrylate, and (4) terpolymers of vinylidene chloride, acrylonitrile or methacrylonitrile and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.
  • the latex polymer is co(vinylidene chloride-methyl acrylate-itaconic acid ; 88 % / 10 % / 2 %).
  • This copolymer is prepared by emulsion polymerization using 0.5 % MERSOLAT H (trade-mark of Bayer AG) as emulsifying agent. It is necessary to add extra surfactant, a so-called post-stabilizer, to the latex in order to assure a good stability on storage. An excellent storage stability is obtained when 4 % of ULTRAVON W, trade mark of Ciba-Geigy, or DOWFAX, trade mark of Dow, is used.
  • colloidal silica may be added as a binder.
  • a preferred compound is KIESELSOL 100F (trade-mark of Bayer AG), average particle size 25-30 nm.
  • the ratio of the amount of latex to silica is preferably about 80/20.
  • the dry thickness of the latex subbing layer is preferably about 0.1 mm.
  • the latex subbing layer of the back side is preferably of similar composition as the latex subbing layer on the upper side.
  • this layer further contains a conductive polymer in order to make the layer antistatic. The nature of this conductive compound will now be explained in detail.
  • Such a compound can show ionic or electronic conductivity.
  • Substances having electronic conductivity instead of ionic conductivity have a conductivity independent from moisture. They are particularly suited for use in the production of antistatic layers with permanent and reproducible conductivity.
  • said polythiophene has thiophene nuclei substituted with at least one alkoxy group, or -O(CH 2 CH 2 O) n CH 3 group, n being 1 to 4, or, most preferably, thiophene nuclei that are ring closed over two oxygen atoms with an alkylene group including such group in substituted form.
  • Preferred polythiophenes for use according to the present invention are made up of structural units corresponding to the following general formula : in which :
  • the most preferred compound is poly(3,4-ethylenedioxythiophene), (PEDT) with following formula :
  • Suitable polymeric polyanion compounds required for keeping said polythiophenes in dispersion are provided by acidic polymers in free acid or neutralized form.
  • the acidic polymers are preferably polymeric sulphonic acids. Examples of such polymeric acids are polymers containing vinyl sulfonic acid and styrene sulfonic acid or mixtures thereof.
  • the anionic acidic polymers used in conjunction with the dispersed polythiophene polymer have preferably a content of anionic groups of more than 2% by weight with respect to said polymer compounds to ensure sufficient stability of the dispersion.
  • Suitable acidic polymers or corresponding salts are described e.g. in DE-A -25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-14 921, EP-A-69 671, EP-A-130 115, US-P 4,147,550, US-P 4,388,403 and US-P 5,006,451.
  • the weight ratio of polythiophene polymer to polymeric polyanion compound(s) can vary widely, for example from about 50/50 to 15/85.
  • polystyrene sulphonate PSS
  • the conductive latex subbing layer has preferably a dry thickness of about 0.1 mm.
  • the gelatin subbing layer is coated on top of the the latex subbing layer on the front side.
  • the gelatin subbing layer preferably contains a mixture of gelatin and colloidal silica.
  • a preferred compound is again KIESELSOL 300F (trade-mark of Bayer AG).
  • a plasticizing compound can be used in order to avoid the formation of cracks in the dried layer due to the occurence of excessive shrinking of the layer during drying.
  • Plasticizing agents are well-known in the art. Low-molecular weight compounds (e.g. acetamide, glycerin) as well as polymeric latices (e.g. polyethylacrylate, poly-n.-butylacrylate) can be used for this purpose.
  • gelatin subbing layer may contain one or more surfactants.
  • useful surfactants include : ULTRAVONTM W, an aryl sulfonate from CIBA-GEIGY, DOWFAX from Dow CO., and ARKOPALTM N060 (previously HOSTAPALTM W), a nonylphenylpolyethylene-glycol from HOECHST.
  • the thickness of the gelatin subbing layer is preferably comprised between 0.1 and 1 ⁇ m.
  • an antihalation layer is present on the back side of the support on top of the latex subbing layer.
  • An antihalation layer contains an antihalation dye and a binder. Antihalation dyes improve the image sharpness by diminishing the upward reflection of light by the support into the emulsion layer.
  • Useful dyes absorbing in the visible spectral region include the coloured piments of US 2,697,037, the pyrazonol oxonol dyes of US 2,274,782, the styryl and butadienyl dyes of US 3,432,207, the diaryl azo dyes of US 2,956,879, the merocyanine dyes of US 2,527,583, the merocyanine and oxonol dyes of US 3,486,897, US 3,652,284 and US 3,718,472, and the enaminohemioxonol dyes of US 3,976,661.
  • Dyes absorbing in the red spectral region of the di- or triphenylmethane type, some of which bear an electron-withdrawing group, are disclosed in e.g. US 2,282,890, DE 1038395, FR 2,234,585, JP-A 59-228250, US 2,252,052 and A. Guyot, Compt. Rend., Vol 114 (1970), p.1120. Some of the compounds disclosed contain one or more water-solubilizing groups.
  • the antihalation dye is non-diffusible under normal coating conditions and only becomes diffusible and/or discolours under alkaline processing conditions.
  • Such dyes can be incorporated as dispersions or as so-called microcrystalline solid particles.
  • Non-diffusible or hardly diffusible dyes of this type are described in e.g. US 4,092,168, EP 274723, EP 276566, EP 294461, EP 299435, GB 1563809, EP 015601, US 4,857,446, JP-A 02-259752, JP-A 02-264247, EP 582753, EP 587229.
  • the antihalation layer is a thin layer having a gelatin coverage of at most 1.5 g/m 2 .
  • the two latex subbing layers, the gelatin subbing layer, and the antihalation layer are coated "on line" in a continuous process in the manufacturing alley of the polyester itself.
  • Molten polyester is extruded and longitudinally stretched.
  • the first latex subbing layer is applied on the upper side
  • the second latex subbing layer, optionally conductive is applied on the back side.
  • the subbed polyester is stretched in the transversal direction.
  • the gelatin subbing layer is applied on the upper side, and finally the antihalation layer is applied on the back side.
  • the emulsion layer(s) and the anti-abrasive layers are coated "off-line". Any well-known coating technique can be used such as dip coating, air-knife coating, slide hopper coating, and curtain coating. In a preferred embodiment the emulsion layer and the two anti-abrasive layers are applied by curtain coating.
  • the polyester support in all examples was a polyethylene terephthalate (PET) support of 100 ⁇ m thickness.
  • PET polyethylene terephthalate
  • composition of the backing subbing layers a first conductive subbing layer containing 180 mg/m 2 of a terpolymer of vinylidene chloride/methyl acrylate/itaconic acid (88%/10%/2%), 20 mg/m 2 of colloidal silica (surface area 100 m 2 /g), and 3.15 mg/m 2 of poly(3,4-ethylenedioxy-thiophene)/ poly(styrene sulphonate) complex; then a gelatin backing layer holding 0.2g of gelatin/m 2 , 0.2 g/m 2 of colloidal silica and 1 mg/m 2 of 3 ⁇ m PMMA (polymethylmethacrylate) matting agent were coated.
  • a first conductive subbing layer containing 180 mg/m 2 of a terpolymer of vinylidene chloride/methyl acrylate/itaconic acid (88%/10%/2%), 20 mg/m 2 of colloidal silica (surface area 100 m 2 /g), and 3.15 mg/m
  • composition of the emulsion side subbing layers a latex subbing layer containing 162 mg/m 2 of a terpolymer of vinylidene chloride/methyl acrylate/itaconic acid (88%/10%/2%), and 40 mg/m 2 of colloidal silica ; then a gelatin subbing layer containing 0.2 g/m 2 of gelatin, 0.2 g/m 2 of colloidal silica, and 1 mg/m 2 of a 3 ⁇ m PMMA matting agent.
  • an aqueous gelatin solution (23.3g gelatin/mol silver) containing sodium chloride
  • an aqueous solution of silver nitrate and an aqueous halide solution containing potassium bromide, sodium chloride, 2.3x10 -7 mol/mol silver of Na 3 RhCl 6 and 3.0x10 -7 mol/mol silver of Na 2 IrCl 6 were added whilst stirring in accordance with a double jet method.
  • a physical ripening was used to form silver chlorobromide grains having an average grain size of 0.27 ⁇ m (variation coefficient: 19%) and a chloride content of 64 mol%. After the physical ripening of the emulsion KI was added to stop crystal growth.
  • the emulsion was washed using a conventional flocculation method, and then redispersed with 33.3 g/mol silver of gelatin.
  • the resulting emulsion was adjusted to pH 5.3 and then chemically sensitized with gold/sulphur at 50°C by digesting during three hours.
  • the emulsion was stabilized with 8.4x10 -3 mol/mol silver of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, and spectrally sensitized with dye SD-1 in an amount of 2.9x10 -4 mol/mol silver.
  • the obtained emulsion had a gelatin/silver ratio of 0.51.
  • the second backing layer contained per m 2 :
  • the emulsion layers were coated simultaneously onto the polyethylene terephthalate film support, using a two layer arrangement with the emulsion layer closest to the support and an anti-abrasion layer on top.
  • the emulsion layer was coated at a pH of 5, with a silver coverage of 3.88 g per square meter of silver. Potassium bromide was added (3.6 mmol/mol silver) to adjust the pAg. To improve curling 300 mg/m 2 of a PEA latex was added. This emulsion layer was then overcoated with an anti-abrasion layer at 1.5 g/m 2 gelatin and further containing formaldehyde as a hardener, hydroquinone and phenidone as stabilizers, coating aids and a PMMA matting agent (3 ⁇ m). After the coating the film sample was dried.
  • composition of the backing subbing layers a latex conductive subbing layer as in example 1, and a gelatin backing layer comprising 1.2 g/m 2 of gelatin, 100 mg/m 2 of AHD-1 as antihalation dye and 10 mg/m 2 of PMMA matting agent (7 ⁇ m) were coated.
  • composition of the emulsion side subbing layers a latex subbing layer containing 162 mg/m 2 of a terpolymer of vinylidene chloride/methyl acrylate/itaconic acid (88%/10%/2%), and 40 mg/m 2 of colloidal silica ; then a gelatin subbing layer holding 0.2 g/m 2 of gelatin, 0.2 g/m 2 of colloidal silica, and 1 mg/m 2 of a 3 ⁇ m PMMA matting agent.
  • an aqueous gelatin solution (23.3 gelatin/mol silver) containing sodium chloride an aqueous solution of silver nitrate and an aqueous halide solution containing potassium bromide, sodium chloride, 2.3x10 -7 mol/mol silver of Na 3 RhCl 6 and 3.0x10 -7 mol/mol silver of Na 2 IrCl 6 were added whilst stirring in accordance with a double jet method.
  • a physical ripening was used to form silver chlorobromide grains having an average grain size of 0.27 ⁇ m (variation coefficient: 19%) and a chloride content of 64 mol%. After the physical ripening of the emulsion KI was added to stop crystal growth.
  • the emulsion was washed using a conventional flocculation method, and then redispersed with 10g gelatin/mol silver.
  • the resulting emulsion was adjusted to pH 5.3 and then chemically sensitized with gold/sulfur at 50°C by digesting during three hours.
  • the emulsion was stabilized with 8.4x10 -3 mol/mol silver of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, spectrally sensitized with dye SD-1 in an amount of 4.0x10 -4 mol/mol silver.
  • the obtained emulsion had a gelatin/silver ratio of 0.31.
  • the emulsion layers were simultaneously coated onto the polyethylene terephthalate film support, using a three layer arrangement with the emulsion layer closest to the support, then an interlayer, and on top an anti-abrasion layer.
  • the emulsion layer was coated at a pH of 5, with a silver coverage of 3.23 g per square meter of silver. Potassium bromide was added (3.6 mmol/mol silver) to adjust pAg.
  • This emulsion layer was overcoated with an interlayer containing 0.5 g/m 2 of gelatin and 0.5 g/m 2 of copoly(AMPS-butylmethacrylate) latex, and hydroquinone and Phenidone as stabilizers.
  • An anti-abrasion layer was coated on top, with 0.5 g/m 2 gelatin containing divinylsulfon hardener, coating aids and a PMMA matting agent.
  • composition of the backing subbing layers a latex conductive subbing layer and a gelatin backing layer comprising 1.2 g of gelatin/m 2 , 100 mg/m 2 of AH-1 as antihalation dye and 10 mg/m 2 7 ⁇ m PMMA matting agent were coated.
  • composition of the emulsion side subbing layers a latex subbing layer containing 162 mg/m 2 of a terpolymer of vinylidene chloride/methyl acrylate/itaconic acid (88%/10%/2%), and 40 mg/m 2 of colloidal silica ; then a gelatin subbing layer holding 0.2 g/m 2 of gelatin, 0.2 g/m 2 of colloidal silica, and 0.025 mg/m 2 of a 1 ⁇ m PMMA matting agent.
  • both backing subbing layers and emulsion side subbing layers were coated during polyesterproduction.
  • an aqueous gelatin solution (16.7 gelatin/mol silver) containing sodium chloride an aqueous solution of silver nitrate and an aqueous halide solution containing potassium bromide, sodium chloride, 2.3x10 -7 mol/mol silver of Na 3 RhCl 6 and 3.0x10 -7 mol/mol silver of Na 2 IrCl 6 were added with stirring in accordance with a double jet method.
  • a physical ripening was used to form silver chlorobromide grains having an average grain size of 0.27 ⁇ m (variation coefficient: 19%) and a chloride content of 64 mol%. After the physical ripening of the emulsion KI was added to stop crystal growth.
  • the emulsion was washed using a conventional flocculation method, and then redispersed with 6.7 g gelatin/mol silver.
  • the resulting emulsion was adjusted to pH 5.3 and then chemically sensitized with gold/sulphur at 50°C by digesting during three hours.
  • the emulsion was stabilized with 8.4x10 -3 mol/mol silver of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, spectrally sensitized with dye SD-1 in an amount of 4.0x10 -4 mol/mol silver.
  • the obtained emulsion had a gelatin/silver ratio of 0.22.
  • the emulsion layers were simultaneously coated onto the polyethylene terephthalate film support, using a three layer arrangement with the emulsion layer closest to the support, then an interlayer and finally an anti-abrasion top layer.
  • the emulsion layer was coated at a pH of 5, with a silver coverage of 2.72 g per square meter of silver. Potassium bromide was added (3.6 mmol/mol silver) to adjust pAg. To improve curling 0.6 g/m 2 of copoly(AMPS-butylmethacrylate) latex was added.
  • This emulsion layer was overcoated with an interlayer comprising 0.5 g/m 2 of gelatin and 0.5 g/m 2 of copoly(AMPS-butylmethacrylate) latex, hydroquinone and Phenidone as stabilizers.
  • An anti-abrasion layer was coated on top, with 0.5 g gelatin/m 2 containing divinylsulfon hardener, 0.8 ml/m 2 of a 20% polyethylene dispersion, coating aids and a PMMA matting agent.
  • composition of the subbing and antihalation layers, and the preparation of the emulsion were the same as in example 3.
  • the emulsion layers were coated simultaneously onto the polyethylene terephthalate film support, using a three layer arrangement with the emulsion layer closest to the support, then an interlayer, and finally an anti-abrasion top layer.
  • the emulsion layer was coated at a pH of 5, with a silver coverage of 2.72 g per square meter of silver. Potassium bromide was added (3.6 mmol/mol silver) to adjust pAg.
  • This emulsion layer was overcoated with an interlayer comprising 0.5 g/m 2 of gelatin and and 0.5 g/m 2 of copoly(AMPS-butylmethacrylate) latex, hydroquinone and Phenidone as stabilizers.
  • An anti-abrasion layer was coated on top, with 0.5 g gelatin/m 2 and further containing divinylsulfon hardener, coating aids and a PMMA matting agent.
  • composition of the subbing and antihalation layers, and the preparation of the emulsion were the same as in example 3 and 4.
  • the emulsion layers were simultaneously coated onto the polyethylene terephthalate film support, using a three layer arrangement with the emulsion layer closest to the support, then an interlayer, and finally an anti-abrasion top layer.
  • the emulsion layer was coated at a pH of 5, with a silver coverage of 2.63 g per square meter of silver.
  • Dextrane was added in an amount of 0.675 ml/m 2 of a 20% solution.
  • Potassium bromide was added (3.6 mmol/mol silver) to adjust pAg.
  • This emulsion layer was overcoated with an interlayer containing 0.5 g/m 2 of gelatin and 0.5 g/m 2 of copoly(AMPS-butylmethacrylate) latex, hydroquinone and Phenidone as stabilizers.
  • An anti-abrasion layer was coated on top, with 0.5 g/m 2 gelatin and further containing divinylsulfon hardener, coating aids and a PMMA matting agent.
  • composition of developer A Composition Value Water 800 ml Potassium carbonate 29.5g Potassium sulfite 34.1 Potasium bromide 2.4 Diethylene glycol 14ml Hydroquinone 17 Sodium erythorbate 2.5 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.275 Methylbenzotriazole 0.06 Water to adjust the volume to 11 Sodium hydroxide to adjust the pH to 10.5
  • the samples were soaked for 2 minutes in water. Afterwards, the water remaining on the surface was removed. The water absorption is the difference in weight before and after.
  • Example Silver-coverage gelatin in emulsion layer latex in emulsion Extra ingredient Note 1 3.88 1.98 15 Comparison 2 3.23 1.00 0 Invention 3 2.72 0.60 50 Invention 4 2.72 0.60 0 Invention 5 2.63 0.53 0 Dextrane Invention Ex. Water-absorption Backing Water-absorption Emulsion Sensitivity Gradation Development speed Covering power Note 1 6.34 g/m 2 5.61 g/m 2 143 328 9 1.49 Comp. 2 0.52 g/m 2 3.74 g/m 2 141 394 7 1.84 Inv. 3 0.52 g/m 2 3.46 g/m 2 143 356 7 1.83 Inv. 4 0.52 g/m 2 3.15 g/m 2 137 428 3 1.82 Inv. 5 0.52 g/m 2 3.19 g/m 2 140 499 9 1.99 Inv.
  • the covering power is increased. So the costprice of the material can be reduced significantly.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
EP00202410A 2000-07-07 2000-07-07 Matériau photographique d'enregistrement Withdrawn EP1170631A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP00202410A EP1170631A1 (fr) 2000-07-07 2000-07-07 Matériau photographique d'enregistrement
US09/891,962 US6432606B1 (en) 2000-07-07 2001-06-26 Photographic recording material
JP2001206070A JP2002040596A (ja) 2000-07-07 2001-07-06 写真記録材料

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3063838A (en) * 1958-11-21 1962-11-13 Du Pont Photographic emulsions and elements containing dextran
US4994353A (en) * 1989-06-15 1991-02-19 Fuji Photo Film Co., Ltd. Silver halide photographic material having polyester support with subbing layer
EP0706082A1 (fr) * 1994-10-06 1996-04-10 Konica Corporation Un matériau photographique à l'halogénure d'argent sensible à la lumière
EP0813105A1 (fr) * 1996-06-13 1997-12-17 Agfa-Gevaert N.V. Matériaux d'enregistrement et procédé de fabrication des dits matériaux couchés des couches hydrophiles n'ayant pas de gélatine ou de taux faibles de gélatine
EP0866366A1 (fr) * 1997-03-21 1998-09-23 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière contenant une couche de substratage ayant une température de transition vitreuse de 40 à 200 degrés Celsius
EP0911694A1 (fr) * 1997-10-20 1999-04-28 Agfa-Gevaert N.V. Un produit photosensible à l'halogénure d'argent comprenant un assemblage de couches

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3063838A (en) * 1958-11-21 1962-11-13 Du Pont Photographic emulsions and elements containing dextran
US4994353A (en) * 1989-06-15 1991-02-19 Fuji Photo Film Co., Ltd. Silver halide photographic material having polyester support with subbing layer
EP0706082A1 (fr) * 1994-10-06 1996-04-10 Konica Corporation Un matériau photographique à l'halogénure d'argent sensible à la lumière
EP0813105A1 (fr) * 1996-06-13 1997-12-17 Agfa-Gevaert N.V. Matériaux d'enregistrement et procédé de fabrication des dits matériaux couchés des couches hydrophiles n'ayant pas de gélatine ou de taux faibles de gélatine
EP0866366A1 (fr) * 1997-03-21 1998-09-23 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière contenant une couche de substratage ayant une température de transition vitreuse de 40 à 200 degrés Celsius
EP0911694A1 (fr) * 1997-10-20 1999-04-28 Agfa-Gevaert N.V. Un produit photosensible à l'halogénure d'argent comprenant un assemblage de couches

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