EP0810468B1 - Lichthofschutzfarbstoff für ein photothermographisches Aufzeichnungsmaterial und dieses Material verwendendes Aufzeichnungsverfahren - Google Patents

Lichthofschutzfarbstoff für ein photothermographisches Aufzeichnungsmaterial und dieses Material verwendendes Aufzeichnungsverfahren Download PDF

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Publication number
EP0810468B1
EP0810468B1 EP97201566A EP97201566A EP0810468B1 EP 0810468 B1 EP0810468 B1 EP 0810468B1 EP 97201566 A EP97201566 A EP 97201566A EP 97201566 A EP97201566 A EP 97201566A EP 0810468 B1 EP0810468 B1 EP 0810468B1
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EP
European Patent Office
Prior art keywords
recording material
substituted
photothermographic recording
antihalation
layer
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EP97201566A
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English (en)
French (fr)
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EP0810468A1 (de
Inventor
Geert Deroover
Etienne Van Thillo
Yvan Hoogmartens
Hans Strijckers
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49872—Aspects relating to non-photosensitive layers, e.g. intermediate protective layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/127—Methine and polymethine dyes the polymethine chain forming part of a carbocyclic ring
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G03C1/49854—Dyes or precursors of dyes
    • 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
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • 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
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/164—Infrared processes

Definitions

  • the present invention relates to a photothermographic recording material comprising specific antihalation dyes and a recording process therefor.
  • Thermal imaging or thermography is a recording process wherein images are generated by the use of imagewise modulated thermal energy.
  • thermography three approaches are known:
  • Thermographic materials of type 1 become photothermographic when a photosensitive agent is present which after exposure to UV, visible or IR light is capable of catalyzing or participating in a thermographic process bringing about changes in colour or optical density.
  • photothermographic materials are the so called “Dry Silver” photographic materials of the 3M Company, which are reviewed by D.A. Morgan in “Handbook of Imaging Science”, edited by A.R. Diamond, page 43, published by Marcel Dekker in 1991.
  • US-P 3,152,904 discloses an image reproduction sheet which comprises a radiation-sensitive heavy metal salt which can be reduced to free metal by a radiation wave length between an X-ray wave length and a five microns wave length and being distributed substantially uniformly laterally over said sheet, and as the image forming component an oxidation-reduction reaction combination which is substantially latent under ambient conditions and which can be initiated into reaction by said free metal to produce a visible change in colour comprising an organic silver salt containing carbon atoms and different from said heavy metal salt as an oxidizing agent and in addition an organic reducing agent containing carbon atoms, said radiation-sensitive heavy metal salt being present in an amount between about 50 and about 1000 parts per million of said oxidation-reduction reaction combination.
  • Photothermographic recording materials may suffer from a phenomenon known as halation which causes degradation in the quality of the recorded image.
  • a portion of the light, which strikes the photosensitive layer but is not absorbed by it, may be reflected back at the interface between the photo-addressable thermally developable element and the support to strike the photo-addressable thermally developable element from the underside.
  • Light thus reflected may, in some cases, contribute significantly to the total exposure of the photo-addressable thermally developable element.
  • Any particulate matter in this element for example particles of organic silver salts and silver halide, may cause light passing through it to be scattered. Scattered light which is reflected from the support will, on its second passage through the photo-addressable thermally developable element, cause exposure over an area adjacent to the point of intended exposure leading to image degradation.
  • EP-A 627 660 and EP-A 681 213 both disclose an infrared antihalation system for a photothermographic silver halide element that satisfies the requirement of an IR (before exposure)/visible absorbance (after processing) 30 : 1 can be achieved with non-bleaching dyes with the following general formula: wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different, each represents substituted or unsubstituted alkyl groups; and each of Z 1 and Z 2 represents a group of non-metallic atoms (e.g.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Z 1 and Z 2 there may be one or more groups having an acid substituent group (e.g. sulfonic group and carboxylic group) or one or more sulfonamide groups.
  • L represents s substituted or unsubstituted methine group;
  • X represents an anion. Examples of the anion represented by X include halogen ions (such as Cl, Br and I), p-toluenesulfonic acid ion and ethyl sulfate ion.
  • n represents 1 or 2.
  • US-P 5,258,282 and JP 04-348 339 discloses indolenine-based pigments according to the general formula given in EP-A 627 660 and EP-A 681 213, but with a wider range of aromatic ring substituents, in association with sensitizing dyes in the heat-developable photosensitive element and in a layer between the heat-developable photosensitive element and the support respectively.
  • a photothermographic material comprising a support; a photo-addressable thermally developable element comprising a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association with the substantially light-insensitive organic silver salt spectrally sensitized to the infrared region of the electromagnetic spectrum and a binder; and in a hydrophobic layer an antihalation dye according to the general formula (I): wherein R 1 and R 15 independently represent an alkyl group or an alkyl group substituted with at least one fluorine, chlorine, bromine or an alkoxy-, aryloxy- or ester-group; R 2 , R 3 , R 16 and R 17 independently represent an alkyl group; R 4 , R 5 , R 6 , R 7 , R 18 , R 19 , R 20 and R 21 independently represent hydrogen, chlorine, bromine, fluorine or a keto-, sulfo-, carboxy-, ester-, sulfonamide-
  • R 1 and R 15
  • a process for the production of the photothermographic recording material referred to above comprising the steps of: (i) loading a polymer latex in an aqueous medium with the antihalation dye by: (I) dissolving the antihalation dye in an organic solvent; (II) adding the antihalation dye solution with stirring to the aqueous medium containing the polymer latex; and (III) evaporating off the organic solvent; and (ii) coating an antihalation layer comprising the antihalation-dye loaded latex and the photo-addressable thermally developable element on the support.
  • a photothermographic recording process comprising the steps of: (i) providing the photothermographic recording material referred to above; (ii) image-wise exposing the photothermographic recording material with actinic radiation to which the photothermographic recording material is sensitive; (iii) bringing the image-wise exposed recording material into proximity with a heat source; (iv) thermally developing the image-wise exposed photothermographic recording material; and (v) removing the thermally developed image-wise exposed recording material from the heat source.
  • the photothermographic material comprises a support, a photo-addressable thermally developable elemtent and in a hydrophobic layer an antihalation dye according to the general formula I.
  • the hydrophobic layer containing the antihalation layer may be an integral part of the photo-addressable thermally developable element or may be a layer separate from this element, may or may not be adjacent to this element and may be on the same side of the support to this element or on the opposite side of the support to this element.
  • Preferred antihalation dyes are represented by formula (I) wherein R 9 and R 10 jointly constitute the atoms necessary to complete a a 5-atom or 6-atom carbocyclic ring and R 13 is chlorine.
  • a - is a fluorinated alkyl or aryl anion in which the degree of fluorination is greater than 70%.
  • anionic dyes can be prepared as described in EP-A 636 493 and US-P 4,973,572 and can be loaded onto a polymer latex in an aqueous medium by adding with stirring a solution of the dye in an organic solvent to the polymer latex dispersion and then evaporating off the organic solvent.
  • Such dye-loaded latexes are not only useful for photothermographic recording materials, but may also be used in a wide range of applications including, for example, thermographic applications utilizing image-wise heating with an infra-red heat source in which such dye-loaded latexes can be used to absorb infrared radiation and convert it into heat or in antihalation layers for such materials and antihalation applications in conventional silver halide emulsion materials.
  • antihalation dyes are:
  • Antihalation dyes may be present in a hydrophobic layer. Antihalation dyes, according to the present invention, may also be present in an antihalation layer not comprising part of the photo-addressable thermally developable element. This antihalation layer may be on the opposite side of the support to the photo-addressable thermally developable element.
  • the photo-addressable thermally developable element comprises a substantially light-insensitive silver salt of a fatty acid, photosensitive silver halide in catalytic association therewith and an organic reducing agent in thermal working relationship with the substantially light-insensitive silver salt of a fatty acid and a binder.
  • the element may comprise a layer system with the silver halide in catalytic association with the substantially light-insensitive organic silver salt ingredients, spectral sensitizer optionally together with a supersensitizer in intimate sensitizing association with the silver halide particles and the other ingredients active in the thermal development process or pre- or post-development stabilization of the element being in the same layer or in other layers with the proviso that the organic reducing agent and the toning agent, if present, are in thermal working relationship with the substantially light-insensitive organic silver salt i.e. during the thermal development process the reducing agent and the toning agent, if present, are able to diffuse to the substantially light-insensitive silver salt of a fatty acid.
  • Preferred substantially light-insensitive organic silver salts according to the present invention are silver salts of organic carboxylic acids in particular aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called "silver soaps"; silver dodecyl sulphonate described in US-P 4,504,575; and silver di-(2-ethylhexyl)-sulfosuccinate described in EP-A 227 141.
  • Modified aliphatic carboxylic acids with thioether group as described e.g.
  • the photosensitive silver halide used in the present invention may be employed in a range of 0.75 to 25 mol percent and, preferably, from 2 to 20 mol percent of substantially light-insensitive organic silver salt.
  • the silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide etc.
  • the silver halide may be in any form which is photosensitive including, but not limited to, cubic, orthorhombic, tabular, tetrahedral, octagonal etc. and may have epitaxial growth of crystals thereon.
  • the silver halide used in the present invention may be employed without modification. However, it may be chemically sensitized with a chemical sensitizing agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc., a reducing agent such as a tin halide etc., or a combination thereof.
  • a chemical sensitizing agent such as a compound containing sulphur, selenium, tellurium etc., or a compound containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc.
  • a reducing agent such as a tin halide etc.
  • a suspension of particles containing a substantially light-insensitive silver salt of an organic carboxylic acid may be obtained by using a process, comprising simultaneous metered addition of an aqueous solution or suspension of an organic carboxylic acid or its salt; and an aqueous solution of a silver salt to an aqueous liquid, as described in EP-A 754 969.
  • the silver halide may be added to the photo-addressable thermally developable element in any fashion which places it in catalytic proximity to the substantially light-insensitive organic silver salt.
  • Silver halide and the substantially light-insensitive organic silver salt which are separately formed, i.e. ex-situ or "preformed", in a binder can be mixed prior to use to prepare a coating solution, but it is also effective to blend both of them for a long period of time.
  • it is effective to use a process which comprises adding a halogen-containing compound to the organic silver salt to partially convert the substantially light-insensitive organic silver salt to silver halide as disclosed in US-P 3,457,075.
  • a particularly preferred mode of preparing the emulsion of organic silver salt and photosensitive silver halide for coating of the photo-addressable thermally developable element from solvent media, according to the present invention is that disclosed in US-P 3,839,049, but other methods such as those described in Research Disclosure, June 1978, item 17029 and US-P 3,700,458 may also be used for producing the emulsion.
  • Suitable organic reducing agents for the reduction of the substantially light-insensitive organic heavy metal salts are organic compounds containing at least one active hydrogen atom linked to O, N or C, such as is the case with, mono-, bis-, tris- or tetrakis-phenols; mono- or bis-naphthols; di- or polyhydroxynaphthalenes; di- or polyhydroxybenzenes; hydroxymonoethers such as alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in US-P 3,094,41; pyrazolidin-3-one type reducing agents, e.g.
  • PHENIDONE (tradename); pyrazolin-5-ones; indan-1,3-dione derivatives; hydroxytetrone acids; hydroxytetronimides; 3-pyrazolines; pyrazolones; reducing saccharides; aminophenols e.g. METOL (tradename); p-phenylenediamines, hydroxylamine derivatives such as for example described in US-P 4,082,901; reductones e.g. ascorbic acids; hydroxamic acids; hydrazine derivatives; amidoximes; n-hydroxyureas; and the like, see also US-P 3,074,809, 3,080,254, 3,094,417 and 3,887,378.
  • aromatic di- and tri-hydroxy compounds having at least two hydroxy groups in para- or ortho-position on the same aromatic nucleus, e.g. benzene nucleus, hydroquinone and hydroquinone derivatives; and catechol and catechol derivatives respectively.
  • Preferred catechol-type reducing agents by which is meant reducing agents containing at least one benzene nucleus with two hydroxy groups (-OH) in ortho-position, include 3-(3',4'-dihydroxyphenyl)propionic acid; pyrogallol; gallic acid; gallic acid esters, e.g.
  • methyl gallate, ethyl gallate and propyl gallate tannic acid; 3,4-dihydroxy-benzoic acid esters; and the polyhydroxyspiro-bis-indane compounds described in US-P 3,440,049, more especially 3,3,3',3'-tetramethyl-5,6,5',6'-tetrahydroxy-1,1'-spiro-bis-indane and 3,3,3',3'-tetramethyl-4,6,7,4',6',7'-hexahydroxy-1,1'-spiro-bis-indane.
  • Particularly preferred catechol-type reducing agents are described in EP-A 692 733.
  • Polyphenols such as the bisphenols used in the 3M Dry SilverTM materials, sulfonamide phenols such as used in the Kodak DacomaticTM materials, and naphthols are particularly preferred for photothermographic recording materials with photo-addressable thermally developable elements on the basis of photosensitive silver halide/organic silver salt/reducing agent.
  • the reducing agent must be present in such a way that it is able to diffuse to the substantially light-insensitive organic silver salt particles so that reduction of the organic silver salt can take place.
  • the silver image density depends on the coverage of the above defined reducing agent(s) and organic silver salt(s) and has to be preferably such that, on heating above 80 °C, an optical density of at least 1.5 can be obtained.
  • an optical density of at least 1.5 can be obtained.
  • at least 0.10 moles of reducing agent per mole of organic heavy metal salt is used.
  • auxiliary reducing agents are e.g. sterically hindered phenols, that on heating become reactive partners in the reduction of the substantially light-insensitive organic heavy metal salt such as silver behenate, such as described in US-P 4,001,026; or are bisphenols, e.g. of the type described in US-P 3,547,648.
  • the auxiliary reducing agents may be present in the imaging layer or in a polymeric binder layer in thermal working relationship thereto.
  • auxiliary reducing agents are sulfonamidophenols are described in the periodical Research Disclosure, February 1979, item 17842, in US-P 4,360,581 and 4,782,004, and EP-A 423 891.
  • Other auxiliary reducing agents that may be used in conjunction with the above mentioned primary reducing agents are sulfonyl hydrazide reducing agents such as disclosed in US-P 5,464,738, trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in US-P 5,496,695 and organic reducing metal salts, e.g. stannous stearate described in US-P's 3,460,946 and 3,547,648.
  • the photo-addressable thermally developable element of the photothermographic recording material may contain a spectral sensitizer, optionally together with a supersensitizer, for the silver halide.
  • the silver halide may be spectrally sensitized with various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes optionally, particularly in the case of sensitization to infrared radiation, in the presence of a so-called supersensitizer.
  • Useful cyanine dyes include those having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus.
  • a basic nucleus such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus.
  • Useful merocyanine dyes which are preferred include those having not only the above described basic nuclei but also acid nuclei, such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus.
  • acid nuclei such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus.
  • imino groups or carboxyl groups are particularly effective.
  • Suitable sensitizers of silver halide to infra-red radiation include those disclosed in the EP-A's 465 078, 559 101, 616 014 and 635 756, the JN's 03-080251, 03-163440, 05-019432, 05-072662 and 06-003763 and the US-P's 4,515,888, 4,639,414, 4,713,316, 5,258,282 and 5,441,866.
  • Suitable supersensitizers for use with infra-red spectral sensitizers are disclosed in EP-A's 559 228 and 587 338 and in the US-P's 3,877,943 and 4,873,184.
  • the film-forming binder for the photo-addressable thermally developable element according to the present invention may be coatable from a solvent or aqueous dispersion medium.
  • the film-forming binder for the photo-addressable thermally developable element according to the present invention may be coatable from a solvent dispersion medium, according to the present invention, may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously: e.g.
  • polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene or mixtures thereof.
  • the film-forming binder for the photo-addressable thermally developable element coatable from an aqueous dispersion medium may be all kinds of transparent or translucent water-dispersible or water soluble natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously for example proteins, such as gelatin and gelatin derivatives (e.g.
  • phthaloyl gelatin cellulose derivatives, such as carboxymethylcellulose, polysaccharides, such as dextran, starch ethers etc., galactomannan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, homo- or co-polymerized acrylic or methacrylic acid, latexes of water dispersible polymers, with or without hydrophilic groups, or mixtures thereof.
  • Polymers with hydrophilic functionality for forming an aqueous polymer dispersion (latex) are described e.g. in US-P 5,006,451, but serve therein for forming a barrier layer preventing unwanted diffusion of vanadium pentoxide present as an antistatic agent.
  • the binder to organic heavy metal salt weight ratio is preferably in the range of 0.2 to 6, and the thickness of the photo-addressable thermally developable element is preferably in the range of 5 to 50 ⁇ m.
  • binders or mixtures thereof may be used in conjunction with waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the reaction speed of the redox-reaction at elevated temperature.
  • heat solvent in this invention is meant a non-hydrolyzable organic material which is in solid state in the recording layer at temperatures below 50°C but becomes a plasticizer for the recording layer in the heated region and/or liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the organic heavy metal salt, at a temperature above 60°C.
  • the photo-addressable thermally developable element contains preferably in admixture with the organic heavy metal salts and reducing agents a so-called toning agent known from thermography or photothermography.
  • Suitable toning agents are succinimide, phthalazine and the phthalimides and phthalazinones within the scope of the general formulae described in US-P 4,082,901. Further reference is made to the toning agents described in US-P 3,074,809, 3,446,648 and 3,844,797.
  • Other particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione described in GB-P 1,439,478 and US-P 3,951,660.
  • a toner compound particularly suited for use in combination with polyhydroxy benzene reducing agents is benzo[e][1,3]oxazine-2,4-dione described in US-P 3,951,660.
  • stabilizers and antifoggants may be incorporated into the photothermographic materials of the present invention.
  • suitable stabilizers and antifoggants and their precursors include the thiazolium salts described in US-P 2,131,038 and 2,694,716; the azaindenes described in US-P 2,886,437 and 2,444,605; the urazoles described in US-P 3,287,135; the sulfocatechols described in US-P 3,235,652; the oximes described in GB-P 623,448; the thiuronium salts described in US-P 3,220,839; the palladium, platinum and gold salts described in US-P 2,566,263 and 2,597,915; the tetrazolyl-thio-compounds described in US-P 3,700,457; the mesoionic 1,2,4-triazolium-3
  • the photo-addressable thermally developable element may contain other additives such as free fatty acids, surface-active agents, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H, silicone oil, e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY), ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, colloidal silica, fine polymeric particles [e.g. of poly(methylmethacrylate)] and/or optical brightening agents.
  • antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
  • silicone oil e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY)
  • the support for the photothermographic recording material according to the present invention may be transparent, translucent or opaque, e.g. having a white light reflecting aspect and is preferably a thin flexible carrier made e.g. from paper, polyethylene coated paper or transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, corona and flame treated polypropylene, polystyrene, polymethacrylic acid ester, polycarbonate or polyester, e.g. polyethylene terephthalate or polyethylene naphthalate as disclosed in GB 1,293,676, GB 1,441,304 and GB 1,454,956.
  • a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the recording material and the paper base substrate.
  • the support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated thermosensitive recording layer.
  • the support may be made of an opacified resin composition, e.g. polyethylene terephthalate opacified by means of pigments and/or micro-voids and/or coated with an opaque pigment-binder layer, and may be called synthetic paper, or paperlike film; information about such supports can be found in EP's 194 106 and 234 563 and US-P's 3,944,699, 4,187,113, 4,780,402 and 5,059,579. Should a transparent base be used, the base may be colourless or coloured, e.g. having a blue colour.
  • One or more backing layers may be provided to control physical properties such as curl or static.
  • the photo-addressable thermally developable element is provided with a protective layer to avoid local deformation of the photo-addressable thermally developable element, to improve its resistance against abrasion and to prevent its direct contact with components of the apparatus used for thermal development.
  • This protective layer may have the same composition as an antisticking coating or slipping layer which is applied in thermal dye transfer materials at the rear side of the dye donor material or protective layers used in materials for direct thermal recording.
  • the protective layer preferably comprises a binder, which may be solvent soluble (hydrophobic), solvent dispersible, water soluble (hydrophilic) or water dispersible.
  • a binder which may be solvent soluble (hydrophobic), solvent dispersible, water soluble (hydrophilic) or water dispersible.
  • hydrophobic binders cellulose acetate butyrate, polymethylmethacrylate and polycarbonates, as described, for example, in EP-A 614 769, are particularly preferred.
  • Suitable hydrophilic binders are, for example, gelatin, polyvinylalcohol, cellulose derivatives or other polysaccharides, hydroxyethylcellulose, hydroxypropylcellulose etc., with hardenable binders being preferred and polyvinylalcohol being particularly preferred.
  • a protective layer of the photothermographic recording material may be crosslinked.
  • Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495 for protective layers, e.g. tetra-alkoxysilanes, polyisocyanates, zirconates, titanates, melamine resins etc., with tetraalkoxysilanes such as tetramethylorthosilicate and tetraethylorthosilicate being preferred.
  • a protective layer according to the present invention may comprise in addition at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant in a binder, wherein at least one of the lubricants is a phosphoric acid derivative, further dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding from the outermost layer.
  • at least one of the lubricants is a phosphoric acid derivative, further dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding from the outermost layer.
  • Such protective layers may also comprise particulate material, e.g. talc particles, optionally protruding from the protective outermost layer as described in WO 94/11198.
  • Other additives can also be incorporated in the protective layer e.g. colloidal particles such as colloidal silica.
  • a photothermographic recording material may have an antistatic layer to prevent charging of the material due to triboelectric contact during coating, transport during finishing and packaging and transport in an apparatus for image-wise exposure and thermal development.
  • an antistatic layer is applied to the opposite side of the support to the photo-addressable thermally developable element.
  • Suitable antistatic layers therefor are described in EP-A's 444 326, 534 006 and 644 456, US-P's 5,364,752 and 5,472,832 and DOS 4125758.
  • Particularly preferred antistatic layers are disclosed in EP-A 628 560, US-P 5,312,681, US-P 5,354,613, US-P 5,372,924, US-P 5,370,981 and US-P 5,391,472.
  • an antihalation dye is incorporated into the antistatic layer.
  • any layer of the photothermographic recording material of the present invention may proceed by any coating technique e.g. such as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc. 220 East 23rd Street, Suite 909 New York, NY 10010, U.S.A.
  • Photothermographic materials may be exposed with radiation of wavelength between an X-ray wavelength and a 5 microns wavelength with the image either being obtained by pixel-wise exposure with a finely focussed light source, such as a CRT light source; a UV, visible or IR wavelength laser, such as a He/Ne-laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm; or a light emitting diode, for example one emitting at 659nm; or by direct exposure to the object itself or an image therefrom with appropriate illumination e.g. with UV, visible or IR light.
  • a finely focussed light source such as a CRT light source
  • a UV, visible or IR wavelength laser such as a He/Ne-laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm
  • a light emitting diode for example
  • any sort of heat source can be used that enables the recording materials to be uniformly heated to the development temperature in a time acceptable for the application concerned e.g. contact heating, radiative heating, microwave heating etc.
  • the photothermographic recording materials of the present invention can be used for both the production of transparencies and reflection type prints.
  • the support will be transparent or opaque, e.g. having a white light reflecting aspect.
  • a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the recording material and the paper base substrate. Should a transparent base be used, the base may be colourless or coloured, e.g. has a blue colour.
  • antihalation dyes D01 to D05 were coated in a layer of LATEX01 onto a polyethylene terephthalate support.
  • the dyes were first dissolved in ethyl acetate, the resulting ethyl acetate solutions were then added to LATEX01 and finally the latex was coated onto a 76 ⁇ m thick polyethylene terephthalate support.
  • the transmission spectra of the layers of INVENTION EXAMPLES 1 to 5 were spectrophotometrically evaluated using a DIANOTM MATCHSCAN spectrophotometer tpo obtain the absorption maxima in the infrared region of the spectrum, ⁇ max , the absorptances of the layers at ⁇ max , D max , and the absorptances at 830nm, D 830 .
  • the values were measured as the infrared material for which the antihalation dyes were being evaluated was intended of use with a 830nm light source.
  • Antihalo-dye Invention example number PMMA coverage mg/m 2 AH-dye coverage mg/m 2 ⁇ max [nm] D max D 830 D02 1 250 11 822 0.092 0.082 D03 2 200 11 881 0.095 D04 3 200 11 822 0.055 0.049 D05 4 200 11 750 0.072 0.038
  • Table 1 demonstrate the suitability of dyes according to the present invention for use as antihalation dyes in hydrophobic layers.
  • PET polyethyleneterephthalate
  • subbing layer consisting of a terpolymer latex of vinylidene chloride-methyl acrylate-itaconic acid (88/10/2) in admixture with colloidal silica (surface area 100m 2 /g).
  • colloidal silica surface area 100m 2 /g.
  • the antihalation/antistatic layers of the photothermographic recording materials of invention examples 5 to 9 were prepared by first adsorbing antihalation dye D01 onto the polymethyl methacrylate particles of LATEX01 by adding different quantities of D01 dissolved in ethyl acetate/g polymethyl methacrylate and then evaporating off the ethyl acetate:
  • the values D 830 were measured as the infrared material with which the antihalation dyes were being used had a maximum spectral sensitivity at about 830nm.
  • a silver halide emulsion consisting of 3.11% by weight of silver halide particles consisting of 97mol% silver bromide and 3mol% silver iodide with an weight average particle size of 50nm, 0.47% by weight of GEL as dispersing agent in deionized water was prepared using conventional silver halide preparation techniques such as described, for example, in T.H. James, "The Theory of the Photographic Process", Fourth Edition, Macmillan Publishing Co. Inc., New York (1977), Chapter 3, pages 88-104.
  • the silver behenate/silver halide emulsion was prepared by adding a solution of 6.8kg of behenic acid in 67L of 2-propanol at 65°C to a 400L vessel heated to maintain the temperature of the contents at 65°C, converting 96% of the behenic acid to sodium behenate by adding with stirring 76.8L of 0.25M sodium hydroxide in deionized water, then adding with stirring 10.5kg of the above-described silver halide emulsion at 40°C and finally adding with stirring 48L of a 0.4M solution of silver nitrate in deionized water. Upon completion of the addition of silver nitrate the contents of the vessel were allowed to cool and the precipitate filtered off, washed, slurried with water, filtered again and finally dried at 40°C for 72 hours.
  • An emulsion layer coating composition for the photothermographic recording materials of invention examples 5 to 9 and comparative example 1 was prepared by adding the following solutions or liquids to 88.15g of the above-mentioned silver behenate/silver halide emulsion in the following sequence with stirring: 0.8g of a 11.5% solution of PHP in methanol followed by a 2 hours stirring, 1g of 2-butanone, 0.2g of a 11% solution of calcium bromide in methanol and 1g of 2-butanone followed by 30 minutes stirring, 0.6g of CBBA, 1.33g of a 0.2% solution of SENSI in 99:1 methanol:triethylamine and 0.04g of MBI followed by 15 minutes stirring, 2.78g of LOWINOXTM 22IB46 and finally 0.5g of TMPS followed by 15 minutes stirring.
  • a protective layer coating compositions for the photothermographic recording materials of invention examples 5 to 9 and comparative example 1 were prepared by dissolving 4.08g of CAB and 0.16g of PMMA in 56.06g of 2-butanone and 5.2g of methanol adding the following solids with stirring in the following sequence: 0.5g of phthalazine, 0.2g of 4-methylphthalic acid, 0.1g of tetrachlorophthalic acid, 0.2g of tetrachlorophthalic acid anhydride.
  • the emulsion layer was then doctor blade-coated at a blade setting of 100 ⁇ m with the protective layer coating composition to a wet layer thickness of 70 ⁇ m, which after drying for 8 minutes at 80°C on an aluminium plate in a drying cupboard produced a layer with the following composition: CAB 4.08g/m 2 PMMA 0.16g/m 2 Phthalazine 0.50g/m 2 4-methylphthalic acid 0.20g/m 2 tetrachlorophthalic acid 0.10g/m 2 tetrachlorophthalic acid anhydride 0.20g/m 2
  • the photothermographic recording materials of invention example 9 and comparative example 1 were exposed to a 849nm single mode diode laser beam from SPECTRA DIODE LABS with a nominal power of 100mW of which 50mW actually reaches the recording material focussed to give a spot diameter (1/e 2 ) of 28 ⁇ m, scanned at speed of 50m/s with a pitch of 14 ⁇ m through a wedge filter with optical density varying between 0 and 3.0 in optical density steps of 0.15.
  • invention examples 10 and 11 were produced as described for invention examples 5 to 9, but with 10mg/m 2 and 15mg/m 2 of D01 respectively with separate coating on a 170 ⁇ m thick polyethylene terephthalate support.
  • the transmission absorption spectra of the protective layers of invention examples 10 and 11 were spectrophotometrically evaluated using a DIANOTM MATCHSCAN spectrophotometer to obtain the absorption maxima in the infrared region of the spectrum, ⁇ max , and the absorptances at 830nm, D 830 .
  • the values D 830 were measured as the infrared material with which the antihalation dyes were being used had a maximum spectral sensitivity at about 830nm.

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Claims (9)

  1. Ein fotothermografisches Aufzeichnungsmaterial, das einen Träger, ein fotoadressierbares thermisch entwickelbares Element mit einem wesentlich lichtunempfindlichen organischen Silbersalz, fotoempfindliches, für das nahe Infrarot des elektromagnetischen Spektrums sensibilisiertes Silberhalogenid in katalytischer Beziehung zum wesentlich lichtunempfindlichen organischen Silbersalz und ein Bindemittel enthält und daneben in einer hydrophoben Schicht einen Lichthofschutzfarbstoff der allgemeinen Formel (I) enthält :
    Figure 00330001
    in der bedeuten :
    R1 und R15 jeweils unabhängig voneinander eine Alkylgruppe oder eine durch wenigstens ein Fluoratom, Chloratom, Bromatom oder eine Alkoxygruppe, Aryloxygruppe oder Estergruppe substituierte Alkylgruppe,
    R2, R3, R16 und R17 jeweils unabhängig voneinander eine Alkylgruppe,
    R4, R5, R6, R7, R18, R19, R20 und R21 jeweils unabhängig voneinander ein Wasserstoffatom, Chloratom, Bromatom, Fluoratom oder eine Keto-, Sulfo-, Carboxy-, Ester-, Sulfonamid-, substituierte Sulfonamid-, Amid-, substituierte Amid-, Dialkylamino-, Nitro-, Cyano-, Alkyl-, substituierte Alkyl-, Alkenyl-, substituierte Alkenyl-, Aryl-, substituierte Aryl-, Alkoxy-, substituierte Alkoxy-, Aryloxy- oder substituierte Aryloxygruppe, wobei jede dieser Gruppen substituiert sein darf, oder R4 zusammen mit R5, R5 zusammen mit R6, R6 zusammen mit R7, R18 zusammen mit R19, R19 zusammen mit R20 oder R20 zusammen mit R21 jeweils unabhängig voneinander die zum Vervollständigen eines gegebenenfalls substituierten Benzolringes benötigten Atome,
    R8, R9, R10 und R11 unabhängig voneinander ein Wasserstoffatom oder eine Alkylgruppe oder R1 zusammen mit R8, R8 zusammen mit R9, R9 zusammen mit R10, R10 zusammen mit R11 oder R11 zusammen mit R15 jeweils unabhängig voneinander die zum Vervollständigen eines gegebenenfalls substituierten, carbocyclischen oder heterocyclischen, 5 oder 6 Atome enthaltenden Ringes benötigten Atome,
    R12, R13 und R14 unabhängig voneinander ein Wasserstoffatom, ein Chloratom, ein Bromatom oder ein Fluoratom, und
    A- ein Anion,
    dadurch gekennzeichnet, daß das Anion ein fluoriertes Alkylanion oder Arylanion mit einem minimalen Fluorierungsgrad von 70% ist.
  2. Fotothermografisches Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß als Bindemittel ein wasserlösliches Bindemittel, ein wasserdispergierbares Bindemittel oder ein Gemisch aus wasserlöslichen und wasserdispergierbaren Bindemitteln benutzt wird.
  3. Fotothermografisches Aufzeichnungsmaterial nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Lichthofschutzfarbstoff der Formel (I) entspricht, in der R9 zusammen mit R10 die zum Vervollständigen eines gegebenenfalls substituierten, carbocyclischen, 5 oder 6 Atome enthaltenden Ringes benötigten Atome darstellen und R13 ein Chloratom ist,
  4. Fotothermografisches Aufzeichnungsmaterial nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Lichthofschutzschicht eine Schicht ist, die an der gegenüberliegenden Seite des Trägers, bezogen auf das fotoadressierbare thermisch entwickelbare Element, aufgetragen ist.
  5. Fotothermografisches Aufzeichnungsmaterial nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Lichthofschutzschicht eine Schicht ist, die an derselben Seite des Trägers, bezogen auf das fotoadressierbare thermisch entwickelbare Element, aufgetragen ist.
  6. Fotothermografisches Aufzeichnungsmaterial nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das wesentlich lichtunempfindliche organische Silbersalz ein Silbersalz einer alifatischen Carbonsäure ist.
  7. Fotothermografisches Aufzeichnungsmaterial nach irgendeinem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das fotoadressierbare thermisch entwickelbare Element mit einer Schutzschicht überzogen ist.
  8. Ein durch die nachstehenden Schritte gekennzeichnetes Verfahren zur Herstellung eines fotothermografischen Aufzeichnungsmaterials nach irgendwelchem der Ansprüche 1 bis 7 : (i) das Beladen eines Polymerlatex in einem wäßrigen Medium mit dem Lichthofschutzfarbstoff durch : (I) Lösen des Lichthofschutzfarbstoffes in einem organischen Lösungsmittel, (II) Einrühren der Lichthofschutzfarbstofflösung in das wäßrige Medium, das den Polymerlatex enthält, und (III) Abdampfen des organischen Lösungsmittels, und (ii) Auftrag einer Lichthofschutzschicht, die den mit dem Lichthofschutzfarbstoff beladenen Latex enthält, und des fotoadressierbaren thermisch entwickelbaren Elements auf den Träger.
  9. Ein durch die nachstehenden Schritte gekennzeichnetes fotothermografisches Aufzeichnungsverfahren : (i) Schaffen eines fotothermografischen Aufzeichnungsmaterials nach irgendwelchem der Ansprüche 1 bis 7, (ii) bildmäßige Belichtung des fotothermografischen Aufzeichnungsmaterials mit aktinischer Strahlung, für die das fotothermografische Aufzeichnungsmaterial empfindlich ist, (iii) Anordnen des bildmäßig belichteten Aufzeichnungsmaterials in der Nähe einer Heizquelle, (iv) Wärmeentwicklung des bildmäßig belichteten fotothermografischen Aufzeichnungsmaterials, und (v) Entfernung des thermisch entwickelten bildmäßig belichteten Aufzeichnungsmaterials von der Heizquelle.
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