EP0250657A1 - Verfahren zur Herstellung eines laminierten Produktes - Google Patents

Verfahren zur Herstellung eines laminierten Produktes Download PDF

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Publication number
EP0250657A1
EP0250657A1 EP86201178A EP86201178A EP0250657A1 EP 0250657 A1 EP0250657 A1 EP 0250657A1 EP 86201178 A EP86201178 A EP 86201178A EP 86201178 A EP86201178 A EP 86201178A EP 0250657 A1 EP0250657 A1 EP 0250657A1
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EP
European Patent Office
Prior art keywords
dye
binder layer
dye image
process according
image
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.)
Granted
Application number
EP86201178A
Other languages
English (en)
French (fr)
Other versions
EP0250657B1 (de
Inventor
Leon Louis Vermeulen
Ludovicus Hendrik Vervloet
Willy Paul De Smedt
Wilhelmus Janssens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
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Agfa Gevaert NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP19860201178 priority Critical patent/EP0250657B1/de
Priority to DE8686201178T priority patent/DE3666635D1/de
Priority to JP16622587A priority patent/JPS6325656A/ja
Publication of EP0250657A1 publication Critical patent/EP0250657A1/de
Application granted granted Critical
Publication of EP0250657B1 publication Critical patent/EP0250657B1/de
Expired legal-status Critical Current

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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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/423—Structural details for obtaining security documents, e.g. identification cards

Definitions

  • the present invention relates to a process for producing a laminar article incorporating a dye image between heat-sealed elements.
  • identification documents contain a black-and-white or colour photograph sandwiched between a clear plastic protective cover sheet and a rear support sheet.
  • the assembly is laminated together to provide a durable identification document, also called ID card.
  • the production of the laminar article through the laminating of a protective thermoplastic or thermohardenable sheet covering the information to be protected proceeds advantageously by heating.
  • the heat applied in the lamination of thermoplastic materials makes that the protective sheet forms a sealed edge with a plastic support underneath.
  • the protective sheet adhesion can be obtained also to the layer containing the image so that it cannot be stripped off without destroying the image.
  • the heat necessary for a firm lamination gives rise to a problem, particularly when the imaging substances are organic dyes produced or applied in silver halide photographic materials.
  • Classical dye formation in silver halide emulsion materials is based on chromogenic development wherein oxidized developing agent couples with coupling agents yielding yellow, magenta and cyan dyes.
  • a more recently developed dye image forming process is based on the image-wise transfer of diffusible dye molecules from an image-wise exposed silver halide emulsion material into a waterpermeable image receiving layer containing a mordant for the dye(s).
  • the image-wise diffusion of the dye(s) is controlled by the development of one or more image-wise exposed silver halide emulsion layers, that for the production of a multicolour image are differently spectrally sensitized and contain respectively a yellow, magenta and cyan dye molecules.
  • a survey of dye diffusion transfer imaging processes has been given by Christian C. Van de Sande in Angew. Chem. - Ed. Engl. 22 (1983) n o 3, 191-209.
  • a process for the production of a laminar article containing a dye image composed of at least one organic dye produced or applied in silver halide photography in a supported hydrophilic binder layer wherein at least a part of said hydrophilic binder layer is heated in a lamination procedure and protected with a protective thermoplastic resin layer or sheet that covers said hydrophilic binder layer containing said dye image, characterized in that said hydrophilic binder layer containing said dye image is treated with an aqueous liquid containing iodide ions that remain in said hydrophilic binder layer during the lamination procedure and form part of said binder layer in the laminar article.
  • the presence of said iodide ions during the heating of the hydrophilic colloid layer containing the dye image counteracts substantially the darkening of the image dye(s) and substantially counteracts the increase of optical density and staining of the whites of the image, i.e. the image background.
  • the free iodide ions are provided by potassium iodide but may stem from any watersoluble metal or onium salt providing iodide ions in aqueous medium.
  • the treatment with iodide ions proceeds preferably with an aqueous liquid containing dissolved potassium iodide in a concentration of 1 to 150 g per liter.
  • the process according to the present invention is not restricted to the production of laminates by heat sealing of a hydrophilic colloid layer containing a dye image produced by a dye diffusion transfer process, but equally applies for dye images obtained by chromogenic development of silver halide using a p-phenylene diamine type developing agent and coupler therefor.
  • the image-receiving layer When forming the dye image in a dye image receiving layer by a dye diffusion transfer process the image-receiving layer can form part of a separate image-­receiving material or form an integral combination with the light-sensitive layer(s) of the photographic material.
  • an alkali-permeable light-shielding layer e.g. containing white pigment particles is applied between the image-receiving layer and the silver halide emulsion layer(s).
  • the image-receiving layer can be composed of or contain basic polymeric mordants such as polymers of amino-guanidine derivatives of vinyl methyl ketone such as described in U.S. Patent Specification 2,882,156, and basic polymeric mordants and derivatives, e.g. poly-4-vinylpyridine, 2-vinylpyridine polymers in salt form and similar compounds described in U.S.
  • Suitable mordanting binders include, e.g. guanylhydrazone derivatives of acyl styrene polymers, as described e.g. in published German Patent Specification 2,631,521.
  • Other effective mordanting compositions are long-chain quaternary ammonium or phosphonium compounds or ternary sulphonium compounds, e.g. those described in US Patent Specifications 3,271,147 and 3,271,148.
  • Certain metal salts and their hydroxides that form sparingly soluble compounds with the acid dyes may be used likewise as mordants.
  • the dye mordants are dispersed in one of the usual hydrophilic binders in the image-receiving layer, e.g. in gelatin, polyvinylpyrrolidone or partly or completely hydrolysed cellulose esters.
  • Preferred polymeric mordants for use in combination with gelatin on a vinyl chloride polymer support are cationic polymeric mordants containing free glycidyl groups that can react with free hydrogen atoms present in gelatin.
  • Such polymeric mordants are described and prepared according to US-P 4,186,014.
  • the following mordant A is a representative thereof :
  • the image-receiving layer which is preferably permeable to alkaline solution, is transparent and about 2 to about 10 um thick. This thickness, of course, can be modified depending upon the result desired.
  • the image-receiving layer may also contain ultraviolet-­absorbing materials to protect the mordanted dye images from fading, brightening agents such as the stilbenes, coumarins, triazines, oxazoles, dye stabilizers such as the chromanols, alkyl-phenols, etc.
  • pH-lowering material in the dye-image-receiving element of a film unit according to the invention will usually increase the stability of the transferred image.
  • the pH-lowering material will effect a reduction of the pH of the image layer from about 13 or 14 to 11 or lower, preferably to a ph of 5 to 8 within a short time after treatment.
  • polymeric acids as disclosed in US Patent Specification 3,362,819 of Edwin H.Land, issued January 9, 1968 or solid acids or metallic salts, e.g. zinc acetate, zinc sulphate, magnesium acetate, etc., as disclosed in US Patent Specification 2,584,030 , my be employed with good results.
  • Such the pH of the film unit after development to terminate development and substantially reduce further dye transfer and thus stabilize the dye image.
  • the hydrophilic colloid layer containing the dye image is treated with an aqueous liquid containing a dissolved surfactant.
  • Said liquid has a cleaning effect and removes organic chemicals stemming from the photographic processing from the dye image containing layer.
  • residual silver halide developing agent e.g. hydroquinone
  • thermoplastic hydrophobic materials e.g, in stacking thin layers of such materials forming one thick sheet, more particularly when at least one of these materials is on the basis of of a vinyl chloride polymer.
  • any commercial surfactant called detergent can be used for said purpose, e.g. a detergent described in the book : "McCutcheon's Detergents & Emulsifiers 1978 North American Edition - McCutcheon Division, MC Publishing Co. 175 Rock Road, Glen Rock, NJ 07452 USA, preference is given to anionic and non-ionic surface-active agents containing a polyethyleneoxide chain in their structure. Examples of such agents are described in US-P 3,663,229.
  • a useful concentration of surfactant for the intended purpose of removing residual organic developing agent is in the range of 5 to 50 g per liter.
  • the layer containing the dye image may be present on any type of support known in photographic materials, e.g. paper, metal or resin support.
  • thermoplastic polyvinyl chloride support According to a preferred embodiment for use in the production of laminates by heat and pressure sealing said layer is present on a thermoplastic polyvinyl chloride support.
  • polyvinyl chloride includes the homopolymer, as well as any vinyl chloride copolymer containing at least 50 % by weight of vinyl chloride units and including no hydrophilic recurring units.
  • Said vinyl chloride copolymer may contain one or more of the following comonomers : vinylidene chloride, vinyl acetate, acrylonitrile, styrene, butadiene, chloroprene, dichlorobutadiene, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, and tetrafluoroethylene.
  • the vinyl chloride polymer serving as the support may be chlorinated to contain 60-65 % by weight of chlorine.
  • polyvinyl chloride and its copolymers are improved by plasticization and their stability can be improved by stabilizers well known to those skilled in the art (see, e.g., F.W.Billmeyer, Textbook of Polymer Chemistry, Interscience Publishers, Inc., New York (1957) p. 311-315)).
  • a corona-discharge surface-treated polyvinyl chloride material serving as a support in the production of a laminated identification card (I.D. card) containing photographic information in a hydrophilic colloid layer is described in US-P 4,429,032.
  • the vinyl chloride polymer support may contain pigments or dyes as colouring matter e.g. in an amount up to 5 % by weight.
  • An opaque white appearance may be obtained with e.g. titanium dioxide particles.
  • the cover sheet used in the lamination process is transparent when the support does not has that property and may be made of any suitable rigid, semirigid or flexible plastic such as a cellulose acetate butyrate, a cellulose triacetate, a polyvinyl chloride, a polymerized polyethylene glycol ester or a polyolefin, or polyolefin-coated polyester, preferably polyethylene-coated polyethyleneglycol terephthalate sheet forming a particularly wear resistant outermost member.
  • any suitable rigid, semirigid or flexible plastic such as a cellulose acetate butyrate, a cellulose triacetate, a polyvinyl chloride, a polymerized polyethylene glycol ester or a polyolefin, or polyolefin-coated polyester, preferably polyethylene-coated polyethyleneglycol terephthalate sheet forming a particularly wear resistant outermost member.
  • thermoplastic sheets may be carried out with hot rollers or plates pressing together the elements to be laminated.
  • the lamination proceeds by introducing the elements to be assembled between flat steel plates under a pressure of 5 to 10 kg per cm2 at a temperature of e.g. from 100 to 150 °C.
  • the laminate may contain the hydrophilic binder layer including the dye image over the whole area of the support or in a part thereof, e.g. leaving free the edge areas as described in US-P 4,101,701 and US-P 4,425,421.
  • a photographic dye diffusion transfer material as described in the Example of US-P 4,496,645 was exposed with white light through a grey wedge having a constant 0.1 and thereupon contacted for 1 minute with an image receiving material having the composition described hereinafter in a diffusion transfer apparatus COPYPROOF CP 38 (trade name of Agfa-Gevaert N.V. Belgium) ) having in its tray a basic processing liquid of the following composition : sodium hydroxide 25 g sodium orthophosphate 25 g cyclohexane dimethanol 25 g 2,2 ⁇ -methylpropylpropane diol 25g N-ethylbenzene-pyridinium chloride 0.5 g distilled water up to 1000 ml - Composition of the image receiving material
  • test materials were laminated with a transparent cover sheet which is a polyethylene terephthalate sheet having a thickness of 100 um being coated at one side with a thermoadhesive layer of polyethylene having a thickness of 30 um.
  • a transparent cover sheet which is a polyethylene terephthalate sheet having a thickness of 100 um being coated at one side with a thermoadhesive layer of polyethylene having a thickness of 30 um.
  • the lamination was carried out between flat steel plates pressing the layers together for 5 minutes using a pressure of 10kg/cm2 at a temperature of 135 °C. Said pressure was maintained during cooling to reach room temperature (20 °C) again.
  • the exposure of the photographic material was carried out as described in Example 1, but using instead of a grey wedge a filter transmitting yellow light and having the optical density (D) versus wavelength (nm) characteristics given in Fig. 3.
  • the yellow dye of the photographic material was transferred into the image receiving layer being present on a white pigmented polyvinyl chloride support.

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  • Engineering & Computer Science (AREA)
  • Computer Security & Cryptography (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19860201178 1986-07-04 1986-07-04 Verfahren zur Herstellung eines laminierten Produktes Expired EP0250657B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP19860201178 EP0250657B1 (de) 1986-07-04 1986-07-04 Verfahren zur Herstellung eines laminierten Produktes
DE8686201178T DE3666635D1 (en) 1986-07-04 1986-07-04 Process for the production of a laminar article
JP16622587A JPS6325656A (ja) 1986-07-04 1987-07-02 積層品の製造方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19860201178 EP0250657B1 (de) 1986-07-04 1986-07-04 Verfahren zur Herstellung eines laminierten Produktes

Publications (2)

Publication Number Publication Date
EP0250657A1 true EP0250657A1 (de) 1988-01-07
EP0250657B1 EP0250657B1 (de) 1989-10-25

Family

ID=8195760

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860201178 Expired EP0250657B1 (de) 1986-07-04 1986-07-04 Verfahren zur Herstellung eines laminierten Produktes

Country Status (3)

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EP (1) EP0250657B1 (de)
JP (1) JPS6325656A (de)
DE (1) DE3666635D1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0351456A1 (de) * 1988-07-07 1990-01-24 Agfa-Gevaert N.V. Verfahren zur Herstellung eines Laminats
EP0380814A1 (de) * 1989-01-31 1990-08-08 Agfa-Gevaert N.V. Verfahren zur Herstellung von Laminaten
GB2321977A (en) * 1997-02-10 1998-08-12 Andrew Cunnigham Thomson Moudable photographic material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1003671A (en) * 1961-08-22 1965-09-08 Eastman Kodak Co Receiving material for photographic dye diffusion transfer process using dye developers
US3249432A (en) * 1960-08-22 1966-05-03 Polaroid Corp Novel photographic processes
DE2339064A1 (de) * 1972-08-04 1974-02-14 Fuji Photo Film Co Ltd Verfahren zur stabilisierung eines photographischen silberhalogenidmaterials
US4101701A (en) * 1973-05-17 1978-07-18 Polaroid Corporation I.D. cards
EP0109111A1 (de) * 1982-11-12 1984-05-23 Agfa-Gevaert N.V. Verfahren zur Herstellung eines farbphotographischen Bildes durch bildmässige Farbstoffdiffusionsübertragung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249432A (en) * 1960-08-22 1966-05-03 Polaroid Corp Novel photographic processes
GB1003671A (en) * 1961-08-22 1965-09-08 Eastman Kodak Co Receiving material for photographic dye diffusion transfer process using dye developers
DE2339064A1 (de) * 1972-08-04 1974-02-14 Fuji Photo Film Co Ltd Verfahren zur stabilisierung eines photographischen silberhalogenidmaterials
US4101701A (en) * 1973-05-17 1978-07-18 Polaroid Corporation I.D. cards
EP0109111A1 (de) * 1982-11-12 1984-05-23 Agfa-Gevaert N.V. Verfahren zur Herstellung eines farbphotographischen Bildes durch bildmässige Farbstoffdiffusionsübertragung

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0351456A1 (de) * 1988-07-07 1990-01-24 Agfa-Gevaert N.V. Verfahren zur Herstellung eines Laminats
EP0380814A1 (de) * 1989-01-31 1990-08-08 Agfa-Gevaert N.V. Verfahren zur Herstellung von Laminaten
GB2321977A (en) * 1997-02-10 1998-08-12 Andrew Cunnigham Thomson Moudable photographic material
GB2321977B (en) * 1997-02-10 2001-10-03 Andrew Cunnigham Thomson Mouldable photographic material
US6544697B2 (en) 1997-02-10 2003-04-08 Digiplast N.V. Mouldable photographic material

Also Published As

Publication number Publication date
DE3666635D1 (en) 1989-11-30
JPS6325656A (ja) 1988-02-03
EP0250657B1 (de) 1989-10-25

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