EP0754970B1 - Verfahren zum Aufbringen von einer hydrophilen Kolloidschicht auf einem Glasträger - Google Patents

Verfahren zum Aufbringen von einer hydrophilen Kolloidschicht auf einem Glasträger Download PDF

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Publication number
EP0754970B1
EP0754970B1 EP96201650A EP96201650A EP0754970B1 EP 0754970 B1 EP0754970 B1 EP 0754970B1 EP 96201650 A EP96201650 A EP 96201650A EP 96201650 A EP96201650 A EP 96201650A EP 0754970 B1 EP0754970 B1 EP 0754970B1
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EP
European Patent Office
Prior art keywords
glass support
support
glass
wetting
hydrophilic colloid
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EP96201650A
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English (en)
French (fr)
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EP0754970A1 (de
Inventor
Jean-Pierre Tahon
Bartholomeus Verlinden
Bart Ramandt
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Agfa Gevaert NV
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Agfa Gevaert NV
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/805—Photosensitive materials characterised by the base or auxiliary layers characterised by stripping layers or stripping means
    • 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
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • 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
    • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
    • G03C1/7954—Polyesters

Definitions

  • This invention relates to a process for applying layers on a naked glass support.
  • this invention relates to silver halide photographic materials applied by lamination onto a glass support.
  • polyester based plastic films can be used to produce photographic materials showing good dimensional stability, it is for speciality applications, e.g. photomicrography, some graphic arts application, photofabrication of PCB (printed circuit boards), etc, still preferred to use silver halide photographic materials coated on glass.
  • the use of a glass support is preferred over the use of a plastic film support.
  • An example of an application where high thermal stability is needed is the manufacture of LCD 's as described in EP-B 396 824 and EP-A 615 161.
  • the optical isotropy of glass is an advantage.
  • It comprises using a liquid feeder having an elastic flexible hanger fitted to its bottom, and control means for keeping a glass plate and the hanger out of contact until the leading edge of the plate passes under the hanger, for putting plate and hanger in contact with each other after the leading edge of the plate has passed under the hanger so that coating is started, and putting plate and hanger out of contact immediately before the liquid is applied to the plate at the trailing edge thereof.
  • This method leaves the leading and trailing margin of a glass plate uncoated and avoid "backside smearing", but requires delicate control of contact and no-contact of the hanger with the glass plates. Further, it easily causes bands and streaks, in particular if the rearside of the hanger becomes soiled.
  • the glass plates are, during the coating process, only supported on the edges. This limits the width of the plates and the thickness of the plates that can be coated in a discontinuous process because wide and thin glass plates that are only supported by the edges bend in the middle and can not easily be coated uniformly. It is possible to design means for supporting thin glass during coating so that the bending in the middle of the glass is avoided (e.g. a supplemental supporting member in the middle of the glass, a full surface support, etc.). The implementation of these additional supporting means in a glass coating machine, however increase the problems for avoiding "backside smearing".
  • Lamination of silver halide photographic materials via an adhesive layer onto glass plates bring about problems in applying an adhesive layer onto the silver halide emulsion layer, in protecting said layer before the lamination by an eventual application of a release foil, in choosing a non colouring adhesive, possible interaction of components of the adhesive layer with photosensitivity of the photographic material, etc.
  • the objects of the invention are realized by providing a method for applying any hydrophilic colloid layer on a naked glass support comprising the steps of :
  • said hydrophilic colloid layer is part of a silver halide photographic material.
  • said hydrophilic colloid layer comprises a proteinaceous colloid and said naked glass support is wetted with a solution comprising an organic silicon compound, comprising a silicon portion having affinity for glass and an organic portion that is tailored to match the reactivity of said proteinaceous colloid.
  • the main advantages of glass as a support for any layer is the dimensional stability of the glass support and the recyclability, the main drawback is the weight of the glass support. Therefore, in many applications, the trend exists to use thinner glass supports to keep the dimensional stability, but to lower the weight of the finished product.
  • the need for glass supports with thickness under 1.2 mm is not uncommon. E.g. in the manufacture of LCD the use of glass supports as thin as 0.7 mm or less is advisable. Especially in this segment, the use of even thinner glass supports is highly desired, both for economical reasons and reasons of weight.
  • a "naked" glass support means hereinafter a glass support on which no special adhesive layer, especially no adhesive layer comprising heat curable or pressure sensitive adhesive compounds, is present.
  • the hydrophilic layer is laminated to said naked glass support so that the hydrophilic layer is in direct contact with the glass support, there is also no need to have an adhesive layer on top of the hydrophilic layer that will be laminated to the glass support. Therefore, when a photographic material is applied to a glass support by a method according to the present invention, no adhesive layers, that usually comprise heat curable or pressure sensitive adhesive as, e.g., film forming copolymers of methyl vinyl ether and maleic anhydride that have been described in US 5,254,447, are present in the photographic material on the glass support. This makes the method especially well suited for the production of photographic materials on glass support that have to withstand yellowing during storage or upon heating of the finished material. Thus this method is especially well suited for the production of photographic materials on glass support for use in the production of colour filters for LCD's.
  • heat curable or pressure sensitive adhesive as, e.g., film forming copolymers of methyl vinyl ether and maleic anhydride that have been described in US 5,254,
  • the method, according to one embodiment of the invention, for laminating at least one hydrophilic colloid layer to a naked glass support comprises two phases :
  • phase I and phase II it is possible to practice phase I and phase II immediately one after another or there may be a lapse of time between phase I and phase II.
  • the method comprises three phases :
  • Phase I and II can be executed separately from phase III or it is possible that phase II is practised separately and that phase I and III can be practised at the same time.
  • the wetting of the naked glass support can proceed with any polar solvent. It can be wetted with water, lower aliphatic alcohols, ketones, dioxane, etc. When wetting the naked glass support with a polar solvent other than water, it is necessary that more than 1 % by volume of water is present in the wetting solution. It is preferred to wet the naked glass support with either ethanol or methanol, comprising more than 1 % by volume of water.
  • a highly useful polar solvent for the wetting solution is a mixture of between 80 and 98 % by volume of ethanol and between 20 and 2 % by volume of water.
  • the wetting solution can comprise surface active compounds. Anionic as well as non-ionic wetting agents are suited therefor.
  • alkyl- and aryl sulphonates such as dodecylsulphonic acid Na-salt, the N-methyl taurinate product with oleic acid (HOSTAPON T) and sulphonated dodecylphenyl phenyl ethers (Dow FAX 2A1, trade name of DOW Chemical, USA), alkyl- and aryl sulphates such as the sodium sulphate of oxethylated nonylphenol (HOSTAPAL B), poly(vinyl alcohol), oxethylated phenols, oleyl alcohol polyglycol ethers, oxethylated polypropylene glycol, etc.
  • HOSTAPON T the N-methyl taurinate product with oleic acid
  • Dow FAX 2A1 sulphonated dodecylphenyl phenyl ethers
  • alkyl- and aryl sulphates such as the sodium sulphate of oxe
  • the hydrophilic colloid layer to be laminated onto a glass support by the method according to the present invention, comprises preferably a proteinaceous colloid and the wetting of the naked glass support proceeds most preferably by a solution comprising an organic silicon compound.
  • Said organic silicon compound comprises a silicon portion having affinity for glass and an organic portion that is tailored to match the reactivity of the hydrophilic colloid (preferably a proteinaceous colloid). In this way the organic silicon compound realizes a stable bond between the glass support and the hydrophilic colloid (preferably a proteinaceous colloid) layer.
  • silicon compounds particularly suitable for use according to the present invention are those corresponding to the following formula, as disclosed in FR-A-2 023 525 : wherein :
  • At least one of said hydrocarbon groups directly connected to the Si atom comprises a group or atom that has a chemical affinity for proteinaceous colloids or that can be cross-linked to the said free reactive groups, present in said proteinaceous colloids, through the intermediary of a cross-linking agent, more particularly a hardening agent commonly used for hardening proteinaceous colloids.
  • R 1 comprises a group or atom that has a chemical affinity for proteinaceous colloids or that can be cross-linked to the said free reactive groups, present in said proteinaceous colloids, through the intermediary of a cross-linking agent, more particularly a hardening agent commonly used for hardening proteinaceous colloids.
  • the other compounds can be prepared as follows.
  • This compound was prepared in an analogous way as compound 2 with the difference, however, that 16.3 g (0.1 mole) of trichloromonoethylsilane were used instead of 19.3 g (0.15 mole) of dichlorodimethylsilane. Boiling point : 138° C/0.5 mm Hg.
  • This compound was prepared in an analogous way as compound 2 with the difference, however, that 29.4 g (0.4 mole) of 2,3-epoxypropanol were used instead of 22.2 g (0.3 mole), 40.4 g (0.4 mole) of triethylamine were used instead of 30.3 g (0.3 mole) and 50.6 g (0.2 mole) of dichloro-diphenylsilane were used instead of 19.3 g (0.15 mole) of dichloro-dimethylsilane. Boiling point : 184° C/0.4 mm Hg.
  • siloxane compounds for use in a method according to the present invention, are siloxanes carrying an epoxy group, the most preferred being compound 4
  • the solvent used to form the wetting solution comprising an organic silicon compound is also preferably a polar solvent. It is possible to wet the naked glass support with a solution, comprising an organic silicon compound that comprises a silicon portion having affinity for glass and an organic portion that is tailored to match the reactivity of the hydrophilic colloid (preferably a proteinaceous colloid), either just before bringing the hydrophilic colloid layer in contact with the wetted glass support, or the naked glass support can be wetted with said solution, dried and after a lapse of time be wetted again with a polar solvent, comprising more than 1 % by volume of water, at the very moment that the hydrophilic colloid layer is brought in contact with the wetted glass support.
  • a polar solvent comprising more than 1 % by volume of water
  • the solvent used to dissolve the silicon containing compound depends on the moment of wetting the naked glass support.
  • the solvent is a polar organic solvent, comprising more than 1 % by volume of water, e.g. dioxane, tetrahydrofuran, acetone, ethylmethylketone, lower aliphatic alcohols, etc. From these solvents lower aliphatic alcohols are preferred, especially preferred are methanol and ethanol.
  • the polar solvent can be water or a mixture of water and an organic polar solvent as described above.
  • a highly useful polar solvent for the wetting solution is a mixture of between 80 and 98 % of ethanol and between 20 and 2 % of water.
  • the wetting solution comprises preferably between 1 and 10 % by weight of organic silicone compounds, more preferably between 3 and 8 % by weight.
  • the wetting solution is preferably applied to the naked glass support such that between 50 mg and 3 g of organic silicon compound are present per m 2 , most preferably between 0.1 and 2 g of organic silicon compound are present per m 2 .
  • wetting solution comprising silicone compounds as described above, may further comprise wetting agents.
  • wetting agents as describe herein above can be used.
  • hardening agents known in the art as suitable for hardening hydrophilic colloids (proteinaceous colloids)
  • Typical hardening agents are, e.g., formaldehyde and divinylsulphones.
  • the wetting solution can be applied to the naked glass support by any technique. It can be sprayed on the support, or coated with the coating techniques known in the art e.g. dip coating, rod coating, blade coating, air knife coating, gravure coating, reverse roll coating, extrusion coating, slide coating and curtain coating.
  • coating techniques known in the art e.g. dip coating, rod coating, blade coating, air knife coating, gravure coating, reverse roll coating, extrusion coating, slide coating and curtain coating.
  • the hydrophilic colloid layers can be any layer comprising a proteinaceous colloid, preferably gelatin. Together with gelatin the layers may comprises other hydrophilic colloids known in the art, e.g. dextrans, polyamides, polyvinylalcohol, cellulose derivatives, polyvinylpyrollidone, synthetic clays, etc.
  • hydrophilic colloids known in the art, e.g. dextrans, polyamides, polyvinylalcohol, cellulose derivatives, polyvinylpyrollidone, synthetic clays, etc.
  • the hydrophilic colloid layers are preferably part of silver halide photographic materials.
  • the silver halide photographic materials that can be applied to a glass support by a method according to the present invention, can be of any type known in the art, e.g. black and white materials, colour materials, materials designed for use in graphic arts, printing plates, materials for use in medical diagnosis, motion picture materials, diffusion transfer materials (both the emulsion layers and the acceptor layer comprising nucleation nuclei), in a dye diffusion transfer process operating with silver halide emulsion layers, etc.
  • the principles and embodiments of silver image formation by DTR-photography are described e.g.
  • the hydrophilic colloid layers can also be subbing layers, antihalation layers, etc.
  • the layers, applied to a glass support by a method according to the present invention form a silver halide photographic material and can comprise any layers know in the art of producing silver halide photographic materials.
  • Such layers are a.o. antihalation layers, intermediate layers, silver halide emulsion layers, protective layers, antistatic layers.
  • the silver halide emulsion layers can comprise a single layer of a silver halide emulsion, or multiple layers of the same or different silver halide emulsions.
  • the silver halide emulsions used in the photographic materials applied to a glass support by a method according to the present invention can comprise any type of photosensitive silver halide, e.g. silver bromide, silver chloride, silver clearheaded, silver bromoiodide or silver chlorobromoiodide or mixtures thereof.
  • the average particle size is preferably in the range of 0.01 to 1.2 ⁇ m.
  • the size distribution of the silver halide particles can be homodisperse or heterodisperse.
  • the crystal habit of the silver halide particles used in silver halide photographic materials applied to a glass support, according to the present invention can be of any type known in the art.
  • the silver halide particles can have a pure cubic or octahedral habit without twin planes. They can also have a mixed cubic/octahedral habit without twin planes.
  • the silver halide crystal particles used in emulsion layers can also contain one or more twin planes, can be tabular as disclosed e.g. in DE 32 41 634 and DE 32 41 640 etc..
  • the light-sensitive silver halide emulsions can be chemically sensitized as described e.g. by P. Glafkidès in “Chimie et Physique Photographique”, Paul Montel, Paris (1987), 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), and in "Die Grundlagen der Photographischen Sawe mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • the light-sensitive silver halide emulsions can be spectrally sensitized with methine 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.
  • the emulsion is preferably not spectrally sensitized in view of the daylight stability.
  • the silver halide emulsion(s), applied on glass supports by a method according to the present invention may be direct positive emulsions, either of the internally desensitized type or of the externally desensitized type comprising spectral desensitizers, e.g. pinakryptol yellow, etc.
  • Said silver halide emulsion(s) 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.
  • the photographic material applied on a glass support by a method according to the present invention, may further comprise various kinds of surface-active agents in the photographic emulsion layer or in another hydrophilic colloid layer.
  • Suitable surface-active agents include non-ionic agents 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 hetero
  • 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.
  • Preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
  • Colour photographic recording materials applied on a glass support by a method according to the present invention, normally comprise at least one silver halide emulsion layer unit for recording light of each of the three spectral regions red, green and blue.
  • colour materials that can be laminated on a glass support bt a method according to the present invention, reference is made to Research Disclosure December 1989, n° 308119 paragraph VII, which is incorporated by reference.
  • the hydrophilic colloid layers to be applied to a glass support fly a method according to the present invention are applied (coated) on a temporary support to form an intermediate photographic element.
  • the uppermost layer i.e. the layer most distant from the temporary support
  • the sequence of the layers is reversed with respect to the sequence the photographic material is intended to have on the final glass support.
  • an AHU antihalation undercoat
  • a protective layer to be an outermost layer
  • the method according to the present invention is especially useful for applying a colour photographic material on to a glass support, especially when this colour photographic material is intended for the production of colour filters for LCD's.
  • Such a method for the production of colour filters for LCD's comprises in consecutive order the steps of :
  • the temporary support for use in the intermediate photographic element to be used in a method according to this invention can be any polymeric support known and commonly employed in the art. They include, e.g. those supports used in the manufacture of photographic films including cellulose acetate propionate or cellulose acetate butyrate, polyesters such as poly(ethyleneterephthalate), polyamides, polycarbonates, polyimides, polyolefins, poly(vinyl acetals), polyethers and polysulfonamides.
  • Polyester film supports and especially poly(ethylene terephthalate) are preferred as temporary support for the image-recording member according to the present invention, because of their excellent properties of dimensional stability. It is preferred to use poly(ethyleneterephthalate) films with a thickness between 40 and 300 ⁇ m as the temporary support for the intermediate photographic member to be used in a method according to the present invention. Most preferably poly(ethyleneterephthalate) films with a thickness between 50 and 100 ⁇ m are used. It is possible to use unsubbed polymeric films as temporary support.
  • a stripping layer can be applied between said temporary support and said hydrophilic colloid layer(s) of the intermediate photographic member.
  • Said stripping layer may be composed as disclosed in e.g. US-P 4,482,625 and EP-A 529697, on the condition that no traces of said stripping layer remain on the photographic material after stripping said temporary support away.
  • a stripping layer for use in an intermediate photographic element according to the present invention comprises preferably either an hydroxyalkylcellulose compound in which alkyl is a C1 to C6 alkylgroup and/or a polyvinylalcohol/polyvinylacetate mixture.
  • the thickness of said stripping layer is in the range of 0.1 to 4 ⁇ m, preferably in the range between 0.5 and 2 ⁇ m.
  • the lamination preferably proceeds in a laminator that offers the possibility to adjust the temperature of the lamination rollers.
  • a laminator is e.g. OLP70 OXAZOL (trade name) of Hoechst AG, Frankfurt, Germany. It is preferred that the lamination rollers have a temperature between 40 and 150 °C, more preferably between 60 and 120 °C.
  • the pressure of the lamination rollers is preferably adjusted to a value between 100 N/m and 1000 N/m for rollers having a shore hardness between 15 and 90 Shore A.
  • the lamination can proceed in conditioned atmosphere; when the atmosphere is conditioned it is preferred to keep the temperature between 20 and 30 °C and the relative humidity between 50 and 99 %, preferably between 75 and 95 %.
  • the lamination can proceed at any speed, it has been found that a good compromise between economics (speed) and lamination quality could be reached when the speed is between 0.1 and 5 m/min.
  • the naked glass support on which is laminated can be any glass of any chemical composition and of any flatness, from from float glass to optical flat glass.
  • glass of high flatness For the purpose of making colour filters for LCD's, it is preferred to use glass of high flatness.
  • the naked glass support can be cut sheets or even a continuous web of very thin glass.
  • thinner glass thickness ⁇ 1.2 mm
  • Young's modulus Young's modulus
  • lamination can proceed after exposure and processing of said photographic member on a temporary support or the lamination can proceed in the absence of actinic light before exposure and the exposure and processing occur after the lamination of the photographic layers on the glass support.
  • a silver chloride-bromide (90/10 molar ratio) emulsion with an average grain size of 0.12 ⁇ m was sensitized to red light with a spectral sensitizing agent of formula SR.
  • a cyan dye forming coupler of formula C1 was added to this emulsion.
  • the amounts of silver halide, gelatin and colour coupler C1 were 0.49, 4.5 and 0.95 g/m 2 respectively.
  • a substance of formula SD capable of scavenging oxidized colour developing agent was dispersed in gelatin and coated at a coverage of 0.08 g SD/m 2 and of 0.77 g gelatine/m 2 .
  • a silver chloride-bromide (90/10 molar ratio) emulsion with an average grain size of 0.12 ⁇ m was sensitized to green light with a spectral sensitizing agent of formula SG.
  • a magenta dye forming coupler of formula M1 was added to this emulsion.
  • the amounts of silver halide, gelatin and colour coupler M1 were 0.71, 2.8 and 0.53 g/m 2 respectively.
  • This layer has the same composition as the first intermediate layer.
  • a 100 % silver chloride emulsion with an average grain size of 0.4 ⁇ m was sensitized to blue light with a spectral sensitizing agent of formula SB.
  • a yellow dye forming coupler of formula Y1 was added to this emulsion.
  • the amounts of silver halide, gelatine and colour coupler Y1 were 0.57, 3.30 and 1.0 g/m 2 respectively.
  • a non-diffusing yellow dye of formula YD was dispersed in gelatin.
  • the coverages of yellow dye YD and gelatin were 0.5 and 1.5 g/m 2 respectively.
  • a naked glass support (sodalime glass) with thickness of 1.2 mm was wetted with demineralized water, without any additive and COLMAT was laminated onto the wetted glass support in a laminator (OLP70 OXAZOL (trade name) of Hoechst AG, Frankfurt, Germany) at a speed of 0.34 m/min.
  • the temperature of the laminating roller was changed :
  • a naked glass support (sodalime glass) with thickness of 1.2 mm was wetted with three different mixtures of a 5 % solution of compound 4 in ethanol (SOL1) and water. The amount of wetting solution was adjusted to have 500 mg of silicon compound per m 2 . COLMAT1 was laminated to the glass.
  • the lamination took place as described above, except that the rollers had a temperature of 100 °C.
  • the wetting solutions had following composition (by volume) :
  • the lamination quality was judged As described above.
  • the adhesion in wet condition was determined as follows : the laminated material, of which the temporary support is stripped away is conditioned for 3 days at a temperature of 20 °C at a relative humidity (RH) of 85 %. Then the materials were soaked in water, the excess water tapped away and the photographic layers were scratched in cross form. After manually rubbing the place were the two scratches cross, the adhesion was visually judged and given a value from 0 (no part of the photographic layer is rubbed away) to 6 (the photographic layers are totally rubbed away).
  • AH Anti-halation
  • AH dyes are present. It is important that during lamination no AH dyes are extracted from COLMAT. The degree of extraction of the AH dyes was judged by measuring the optical density of the dyes in COLMAT and then measuring the optical density of the dyes in LAM 4, LAM 5 and LAM 6. The measurement proceeded after a red filter measuring the green AH dye and after a green filter measuring the red AH dye. The difference in density ( ⁇ D) is a measure for the extraction of the dyes.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)

Claims (12)

  1. Ein Verfahren zum direkten Aufbringen einer hydrophilen Kolloidschicht auf einen unbeschichteten Glasträger, mit folgenden Stufen :
    (i) die Benetzung eines unbeschichteten Glasträgers mit einer Netzlösung, die ein polares Lösungsmittel und wenigstens 1 Vol.-% Wasser enthält, mit der Maßgabe, daß die Netzlösung keine polymere haftende Verbindung enthält,
    (ii) den Auftrag der hydrophilen, auf einen zeitweiligen Träger aufgetragen Kolloidschicht auf den benetzten Glasträger, wobei die hydrophile Kolloidschicht in direktem Kontakt mit dem benetzten Glas kommt, und
    (iii) das Abziehen des zeitweiligen Trägers.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Netzlösung weiterhin eine organische Siliciumverbindung enthält.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die organische Siliciumverbindung der Formel
    Figure 00320001
    entspricht,
    in der bedeuten :
    X ein Sauerstoffatom oder -O-CO-,
    R1, R2, R3 und R4 (gleich oder verschieden) jeweils eine gegebenenfalls substituierte Kohlenwasserstoffgruppe wie eine Alkylgruppe und eine Arylgruppe, wobei wenigstens eine der Kohlenwasserstoffgruppen eine Gruppe oder ein Atom enthält, die bzw. das eine chemische Affinität zu proteinartigen Kolloiden aufweist oder mit Hilfe eines Vernetzungsmittels, insbesondere eines üblicherweise zur Härtung von proteinartigen Kolloiden benutzten Härters, zu freien, in den proteinartigen Kolloiden enthaltenen reaktionsfähigen Gruppen vernetzt werden kann, und n, n' und n" (gleich oder verschieden) jeweils 0 oder 1, wobei n + n' + n" wenigstens gleich 1 ist.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß n + n' + n" gleich 3 ist und R1 eine Gruppe oder ein Atom enthält, die bzw. das eine chemische Affinität zu proteinartigen Kolloiden aufweist oder mit Hilfe eines Vernetzungsmittels, insbesondere eines üblicherweise zur Härtung von proteinartigen Kolloiden benutzten Härters, zu den freien, in den proteinartigen Kolloiden enthaltenen reaktionsfähigen Gruppen vernetzt werden kann.
  5. Verfahren nach irgendeinem der Ansprüche 2 bis 4, dadurch gekennzeichnet, daß die organische Siliciumverbindung eine Epoxygruppe enthält.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die organische Siliciumverbindung der Formel
    Figure 00330001
    entspricht.
  7. Verfahren nach irgendeinem der obigen Ansprüche, dadurch gekennzeichnet, daß die Netzlösung ein polares, aus einem Gemisch aus zwischen 80 und 98 Vol.-% Ethanol und zwischen 20 und 2 Vol.-% Wasser zusammengesetztes Lösungsmittel enthält.
  8. Verfahren nach irgendeinem der Ansprüche 2 bis 7, dadurch gekennzeichnet, daß die Netzlösung zwischen 1 und 10 Gew.-% der organischen Siliciumverbindung enthält.
  9. Verfahren nach irgendeinem der obigen Ansprüche, dadurch gekennzeichnet, daß die Benetzung dadurch erfolgt, daß die Netzlösung in solcher Menge auf den unbeschichteten Glasträger vergossen wird, daß pro Quadratmeter zwischen 50 mg und 3 g organische Siliciumverbindung enthalten sind.
  10. Verfahren nach irgendeinem der obigen Ansprüche, dadurch gekennzeichnet, daß der zeitweilige Träger eine Poly(ethylenterephthalat)-Folie mit einer Stärke zwischen 40 und 300 µm ist.
  11. Verfahren nach irgendeinem der obigen Ansprüche, dadurch gekennzeichnet, daß das Verfahren bei einer Temperatur zwischen 40 und 150°C ausgeführt wird.
  12. Ein Verfahren zum Aufbringen einer beliebigen hydrophilen Kolloidschicht auf einen unbeschichteten Glasträger, wobei das Verfahren drei Phasen umfaßt :
    In Phase I wird wenigstens eine hydrophile Schicht auf einen zeitweiligen, ein Zwischenelement bildenden Träger vergossen,
    Phase II umfaßt folgende Stufen :
    (i) die Benetzung eines unbeschichteten Glasträgers mit einer Netzlösung, die ein polares Lösungsmittel, mehr als 1 Vol.-% Wasser und eine organische Siliciumverbindung enthält, mit der Maßgabe, daß die Netzlösung keine polymere haftende Verbindung enthält, wobei die organische Siliciumverbindung einen Siliciumanteil mit Affinität zu Glas und einen organischen Anteil, dessen Reaktivität der Reaktivität des proteinartigen Kolloids entspricht, enthält, und
    (ii) die Trocknung des Trägers bei einer Temperatur über 50°C, wodurch ein vorbehandelter Glasträger erhalten wird, und
    Phase III umfaßt folgende Stufen :
    (i) die Benetzung des vorbehandelten Glasträgers mit einer Netzlösung, die ein polares, wenigstens 1 Vol.-% Wasser enthaltendes Lösungsmittel enthält, mit der Maßgabe, daß die Netzlösung keine polymere haftende Verbindung enthält,
    (ii) den Auftrag des Zwischenelements auf den benetzten Glasträger, wobei die hydrophile Kolloidschicht in direktem Kontakt mit dem Glasträger kommt, wodurch eine komplexe Struktur entsteht, und
    (iii) das Abziehen des zeitweiligen Trägers.
EP96201650A 1995-07-14 1996-06-13 Verfahren zum Aufbringen von einer hydrophilen Kolloidschicht auf einem Glasträger Expired - Lifetime EP0754970B1 (de)

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GB1286467A (en) * 1968-11-18 1972-08-23 Agfa Gevaert Proteinaceous colloid compositions and their adherence to glass supports
DD144131A1 (de) * 1979-05-31 1980-09-24 Martin Scharf Fotografische materialien mit lichthofschutz auf basis von halogensilberemulsionen
EP0529697B1 (de) * 1991-07-12 1995-05-24 Agfa-Gevaert N.V. Abziehfilmmaterial
US5254447A (en) * 1992-04-20 1993-10-19 Eastman Kodak Company Photographic elements comprising a glass plate support and method for their manufacture

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