EP1598207B1 - Stabilisatoren zur Verwendung in thermographischen Aufzeichnungsmaterialien die im wesentlichen lichtunempfindlich sind - Google Patents

Stabilisatoren zur Verwendung in thermographischen Aufzeichnungsmaterialien die im wesentlichen lichtunempfindlich sind Download PDF

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EP1598207B1
EP1598207B1 EP05102620A EP05102620A EP1598207B1 EP 1598207 B1 EP1598207 B1 EP 1598207B1 EP 05102620 A EP05102620 A EP 05102620A EP 05102620 A EP05102620 A EP 05102620A EP 1598207 B1 EP1598207 B1 EP 1598207B1
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groups
group
alkyl
mbiz
substantially light
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French (fr)
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EP1598207A1 (de
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Frank Agfa-Gevaert LOUWET
Johan Agfa-Gevaert Loccufier
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Agfa HealthCare NV
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Agfa HealthCare NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
    • 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
    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • 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
    • G03C1/49863—Inert additives, e.g. surfactants, binders
    • 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
    • G03C2200/00—Details
    • G03C2200/40—Mercapto compound

Definitions

  • the present invention concerns stabilizers for use in substantially light-insensitive thermographic recording materials.
  • Thermography is an image-forming process including a heating step and hence includes photothermography in which the image-forming process includes image-wise exposure and direct thermal processes in which the image-forming process includes an image-wise heating step.
  • direct thermal printing a visible image pattern is produced by image-wise heating of a recording material.
  • EP-A 0 901 040 discloses a substantially light-insensitive monosheet recording material comprising a support and a thermosensitive element containing a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith and a binder, characterized in that said thermosensitive element further contains an unsaturated carbocyclic or heterocyclic stabilizer compound substituted with a -SA group where A is hydrogen, a counterion to compensate the negative charge of the thiolate group or a group forming a symmetrical or an asymmetrical disulfide and said recording material is capable of producing prints with a numerical gradation value defined as the quotient of the fraction (2.5 - 0.1)/(E 2.5 - E 0.1 ) greater than 2.3, where E 2.5 is the energy in Joule applied in a dot area of 87 ⁇ m x 87 ⁇ m of the imaging layer that produces an optical density value of 2.5, and E 0.1 is the energy in Joule applied in a dot area of the
  • EP-A 0 897 130 discloses a thermographic recording element having at least one image forming layer, said element comprising an organic silver salt, a reducing agent, and at least one of the substituted alkene derivatives of the general formulae (1) through (14): wherein W is an electron attractive group, D is an electron donative group, H is hydrogen, the groups represented by W or D attached to the same carbon atom, taken together, may form a cyclic structure, the compound may assume either a trans or cis structure when both trans and cis structures are possible with respect to W or D, and two W groups in formula (14) form a cyclic structure.
  • US 3,839,041 discloses a photothermographic element comprising a support having thereon photosensitive silver halide in association with an oxidation-reduction image-forming combination comprising (i) a heavy metal salt oxidizing agent with (ii) a reducing agent, a binder, and a stabilizer precursor which is a compound of the formula: Wherein R 3 is acetyl, propionyl, butyryl, pentanoyl, carboxy, cyano, aroyl containing up to 13 carbon atoms, or furyl; R 5 is alkyl containing one to five carbon atoms, carboxy, aryl containing six to 12 carbon atoms, or hydrogen; R 4 is alkyl containing one to five carbon atoms, carboxy, or hydrogen; n is 0 or 2.
  • thermographic recording materials Differences between substantially light-insensitive thermographic recording materials and photothermographic recording materials
  • thermographic materials in which image formation is based on the reduction of organic silver salts is significantly different from that of photothermographic recording materials, despite the fact that in both cases the image results from the reduction of organic silver salts.
  • this a superficial similarity masking the fact that the realization of the species which catalyze this reduction is completely different, being image-wise exposure of photosensitive silver halide-containing photo-addressable thermally developable elements in the case of photothermographic recording materials and image-wise heating of thermosensitive elements which do not contain photosensitive silver halide in the case of thermographic recording materials.
  • Substantially light-insensitive thermographic recording materials contain the imaging-forming components both before and after image formation and unwanted image-forming must be hindered both during storage prior to printing and in prints exposed to light on light-boxes e.g. during examination by radiologists. Furthermore, such stabilization must take place without adverse effects upon the image quality particularly the image tone. There is therefore a need for stabilizers which fulfil these requirements.
  • thermographic recording materials which endow substantially light-insensitive thermographic recording materials with improved image tone stability of the image background upon exposure to light, particularly in respect of b* CIELAB values.
  • thermographic recording materials suitable with improved image tone stability of the image background after storage, particularly in respect of b* CIELAB values.
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
  • the L*, a* and b* CIELAB-values are defined in ASTM Norm E179-90 in a R(45/0) geometry with evaluation according to ASTM Norm E308-90.
  • Substantially light-insensitive means not intentionally light sensitive.
  • thermosensitive element as used herein is that element which contains all the ingredients which contribute to image formation.
  • the thermosensitive element contains one or more substantially light-insensitive organic silver salts, one or more reducing agents therefor in thermal working relationship therewith and at least one binder.
  • the element may comprise a layer system in which the above-mentioned ingredients may be dispersed in different layers, with the proviso that the substantially light-insensitive organic silver salts are in reactive association with the reducing agents i.e. during the thermal development process the reducing agent must be present in such a way that it is able to diffuse to the particles of substantially light-insensitive organic silver salt so that reduction to silver can occur.
  • thermosensitive element of the substantially light-insensitive black and white monosheet thermographic recording material preferably excludes at least one of the substituted alkene derivatives of the general formulae (1) through (14): wherein W is an electron attractive group, D is an electron donative group, H is hydrogen, the groups represented by W or D attached to the same carbon atom, taken together, may form a cyclic structure, the compound may assume either a trans or cis structure when both trans and cis structures are possible with respect to W or D, and two W groups in formula (14) form a cyclic structure.
  • the substantially light-insensitive black and white monosheet thermographic recording material includes the possibility of one or more substantially light-insensitive organic silver salts and/or one of more organic reducing agents therefor being encapsulated in heat-responsive microcapsules, such as disclosed in EP-A 0 736 799 .
  • n is at least 1.
  • A is selected from the group consisting of an optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, optionally substituted alkyaryl groups, optionally substituted alkyl-heterocyclic groups, optionally substituted alkyl-heteroaromatic groups, optionally substituted alkyl groups in which at least one of the non-terminal main chain carbon atoms is substituted with an oxygen or a sulfur atom, optionally substituted aryl groups, optionally substituted alkyl-aryl-alkyl groups, optionally substituted alkyl-heteroaryl-alkyl groups, optionally substituted alkyl-COO-alkyl-OOC-alkyl groups, optionally substituted alkyl-O-COO-alkyl groups, optionally substituted alkyl-CON
  • X is -A-M and -M is a -(2-S-imidazole) group or a -(2-S-imidazole) group annelated with an aromatic ring system.
  • X is -A-(CH 2 ) m -M, wherein m is 2 to 20 and -M is a -(2-S-imidazole) group or a -(2-S-imidazole) group annelated with an aromatic ring system.
  • X is -A-(CH 2 ) m -M, wherein m is 4 to 9 and -M is a -(2-S-imidazole) group or a -(2-S-imidazole) group annelated with an aromatic ring system.
  • the at least one stabilizer represented by formula (I) is selected from the group consisting of:
  • the at least one stabilizer represented by formula (I) is selected from the group consisting of:
  • Suitable compounds represented by formula (I), according to the present invention include: Structure MBIZ-1 MBIZ-2 MBIZ-3 MBIZ-4 MBIZ-5 MBIZ-6 MBIZ-7 MBIZ-8 MBIZ-9 MBIZ-10 MBIZ-11 MBIZ-12 MBIZ-13 MMIZ-1 MMIZ-2 MMIZ-3 MMIZ-4 MMIZ-5 MMIZ-6
  • the organic silver salts are not double organic salts containing a silver cation associated with a second cation e.g. magnesium or iron ions.
  • At least one of the organic silver salts is a substantially light-insensitive silver salt of an organic carboxylic acid.
  • At least one of the organic silver salts is a substantially light-insensitive silver salt of an aliphatic carboxylic acids known as a fatty acid, 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".
  • Other silver salts of an organic carboxylic acid as described in GB-P 1,439,478 e.g. silver benzoate, may likewise be used to produce a thermally developable silver image.
  • Combinations of different silver salt of an organic carboxylic acids may also be used in the present invention, as disclosed in EP-A 964 300 .
  • Organic silver salts may be dispersed by standard dispersion techniques. Ball mills, bead mills, microfluidizers, ultrasonic apparatuses, rotor stator mixers etc. have been found to be useful in this regard. Mixtures of organic silver salt dispersions produced by different techniques may also be used to obtain the desired thermographic properties e.g. of coarser and more finely ground dispersions of organic silver salts.
  • the reducing agent is an organic compound containing at least one active hydrogen atom linked to O, N or C, such as is the case with, aromatic di- and tri-hydroxy compounds.
  • 1,2-dihydroxybenzene derivatives such as catechol, 3-(3,4-dihydroxyphenyl) propionic acid, 1,2-dihydroxybenzoic acid, gallic acid and esters e.g. methyl gallate, ethyl gallate, propyl gallate, tannic acid, and 3,4-dihydroxy-benzoic acid esters are preferred, with those described in EP-A 0 692 733 and EP-A 0 903 625 being particularly preferred.
  • Combinations of reducing agents may also be used that on heating become reactive partners in the reduction of the one or more substantially light-insensitive organic silver salt.
  • combinations of sterically hindered phenols with sulfonyl hydrazide reducing agents such as disclosed in US 5,464,738 ; trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in US 5,496,695 ; trityl hydrazides and formyl-phenyl-hydrazides with diverse auxiliary reducing agents as disclosed in US 5,545,505 , US 5,545,507 and US 5,558,983 ; acrylonitrile compounds as disclosed in US 5,545,515 and US 5,635,339 ; and 2-substituted malonodialdehyde compounds as disclosed in US 5,654,130 .
  • thermosensitive element Binder of the thermosensitive element
  • the film-forming binder of the thermosensitive element may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, in which the at least one organic silver salt can be dispersed homogeneously either in aqueous or solvent media: e.g.
  • cellulose derivatives starch ethers, galactomannan, 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 alcohol, 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, polyacrylates, polymethacrylates, polystyrene and polyethylene or mixtures thereof.
  • aldehyde preferably polyvinyl butyral
  • copolymers of acrylonitrile and acrylamide copolymers of acrylonitrile and
  • the at least one binder comprises at least one first polymer consisting of vinyl aceto-acetal monomer units and monomer units selected from the group consisting of vinyl butyral, vinyl alcohol, vinyl acetate and itaconic acid monomer units, wherein the weight ratio of the at least one binder to said light-insensitive silver salt(s) of a carboxylic acid in said thermosensitive element is greater than 1.5; and the at least one binder optionally contains less than 40% by weight of a second polymer consisting of vinyl butyral monomer units and optionally vinyl alcohol and/or vinyl acetate monomer units.
  • thermographic recording materials are: polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone, polyethyleneglycol, proteinaceous binders, polysaccharides and water-soluble cellulose derivatives.
  • a preferred water-soluble binder for use in the thermographic recording materials of the present invention is gelatine.
  • the binder to organic silver salt weight ratio is preferably in the range of 0.2 to 7, and the thickness of the thermosensitive element is preferably in the range of 5 to 50 ⁇ m. Binders are preferred which do not contain additives, such as certain antioxidants (e.g. 2,6-di-tert-butyl-4-methylphenol), or impurities which adversely affect the thermographic properties of the thermographic recording materials in which they are used.
  • additives such as certain antioxidants (e.g. 2,6-di-tert-butyl-4-methylphenol), or impurities which adversely affect the thermographic properties of the thermographic recording materials in which they are used.
  • thermosensitive element contains a toning agent, which enables a neutral black image tone to be obtained in the higher densities and neutral grey in the lower densities.
  • thermosensitive element further contains a toning agent selected from the group consisting of phthalimides, phthalazinones, benzoxazine diones and naphthoxazine diones e.g.
  • phthalimides and phthalazinones within the scope of the general formulae described in US 4,082,901 ; the toning agents described in US 3,074,809 , 3,446,648 and 3,844,797 ; and the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type as disclosed in GB 1,439,478 , US 3,951,660 and US 5,599,647 .
  • the substantially light-insensitive thermographic recording material contains a thermosensitive element, the thermosensitive element containing one or more toning agents selected from the group consisting of phthalazinone, benzo [e] [1,3] oxazine-2,4-dione, 7-methyl-benzo[e][1,3]oxazine-2,4-dione, 7-methoxy-benzo[e][1,3]oxazine-2,4-dione and 7-(ethylcarbonato)-benzo[e][1,3]oxazine-2,4-dione.
  • phthalazinone benzo [e] [1,3] oxazine-2,4-dione
  • 7-methyl-benzo[e][1,3]oxazine-2,4-dione 7-methoxy-benzo[e][1,3]oxazine-2,4-dione
  • thermographic recording material further contains an auxiliary antifoggant to obtain improved shelf-life and reduced fogging.
  • thermographic recording material further contains an antifoggant selected from the group consisting of benzotriazole, substituted benzotriazoles and aromatic polycarboxylic acid such as ortho-phthalic acid, 3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid, pyromellitic acid and trimellitic acid and anhydrides thereof.
  • an antifoggant selected from the group consisting of benzotriazole, substituted benzotriazoles and aromatic polycarboxylic acid such as ortho-phthalic acid, 3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid, pyromellitic acid and trimellitic acid and anhydrides thereof.
  • thermosensitive element further contains an optionally substituted benzotriazole.
  • the thermosensitive element further contains at least one polycarboxylic acid and/or anhydride thereof in a molar percentage of at least 15 with respect to all the organic silver salt(s) present and in thermal working relationship therewith.
  • the polycarboxylic acid may be aliphatic (saturated as well as unsaturated aliphatic and also cycloaliphatic) or an aromatic polycarboxylic acid, may be substituted and may be used in anhydride form or partially esterified on the condition that at least two free carboxylic acids remain or are available in the heat recording step.
  • the substantially light-insensitive thermographic material used in the present invention may contain one or more surfactants, which may be anionic, non-ionic or cationic surfactants and/or one or more dispersants.
  • Suitable dispersants are natural polymeric substances, synthetic polymeric substances and finely divided powders, e.g. finely divided non-metallic inorganic powders such as silica.
  • the support is transparent or translucent. It is preferably a thin flexible carrier made transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. polyethylene terephthalate.
  • the support may be in sheet, ribbon or web form and subbed if needs be to improve the adherence to the thereon coated thermosensitive element.
  • the support may be dyed or pigmented to provide a transparent coloured background for the image.
  • the thermosensitive element is provided with a protective layer.
  • a protective layer In general this protects the thermosensitive element from atmospheric humidity and from surface damage by scratching etc. and prevents direct contact of printheads or heat sources with the recording layers.
  • Protective layers for thermosensitive elements which come into contact with and have to be transported past a heat source under pressure, have to exhibit resistance to local deformation and good slipping characteristics during transport past the heat source during heating.
  • a slipping layer being the outermost layer, may comprise a dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding from the outermost layer. Examples of suitable lubricating materials are a surface active agent, a liquid lubricant, a solid lubricant or mixtures thereof, with or without a polymeric binder.
  • any layer of the substantially light-insensitive thermographic material used in 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, USA. Coating may proceed from aqueous or solvent media with overcoating of dried, partially dried or undried layers.
  • Thermographic imaging is carried out by the image-wise application of heat either in analogue fashion by direct exposure through an image or by reflection from an image, or in digital fashion pixel by pixel either by using an infra-red heat source, for example with a Nd-YAG laser or other infra-red laser, with a substantially light-insensitive thermographic recording material preferably containing an infra-red absorbing compound, or by direct thermal imaging with a thermal head.
  • an infra-red heat source for example with a Nd-YAG laser or other infra-red laser
  • a substantially light-insensitive thermographic recording material preferably containing an infra-red absorbing compound
  • thermal printing image signals are converted into electric pulses and then through a driver circuit selectively transferred to a thermal printhead.
  • the thermal printhead consists of microscopic heat resistor elements, which convert the electrical energy into heat via Joule effect.
  • the operating temperature of common thermal printheads is in the range of 300 to 400°C and the heating time per picture element (pixel) may be less than 1.0ms, the pressure contact of the thermal printhead with the recording material being e.g. 200-1000g/linear cm, i.e. with a contact zone (nip) of 200 to 300 ⁇ m a pressure of 5000 to 50,000 g/cm 2 , to ensure a good transfer of heat.
  • the image-wise heating of the recording material with the thermal printing heads may proceed through a contacting but removable resin sheet or web wherefrom during the heating no transfer of recording material can take place.
  • Activation of the heating elements can be power-modulated or pulse-length modulated at constant power.
  • EP-A 654 355 discloses a method for making an image by image-wise heating by means of a thermal head having energizable heating elements, wherein the activation of the heating elements is executed duty cycled pulsewise.
  • EP-A 622 217 discloses a method for making an image using a direct thermal imaging element producing improvements in continuous tone reproduction.
  • Image-wise heating of the recording material can also be carried out using an electrically resistive ribbon incorporated into the material.
  • Image- or pattern-wise heating of the recording material may also proceed by means of pixel-wise modulated ultrasound.
  • Thermographic imaging can be used for the production of reflection type prints and transparencies, in particular for use in the medical diagnostic field in which black-imaged transparencies are widely used in inspection techniques operating with a light box.
  • Subbing layer Nr. 01 on the emulsion side of the support copolymer of 88% vinylidene chloride, 10% methyl acrylate and 2% itaconic acid 79.1 mg/m 2 Kieselsol ® 100F, a colloidal silica from BAYER 18.6 mg/m 2 Mersolat ® H, a surfactant from BAYER 0.4 mg/m 2 Ultravon ® W, a surfactant from CIBA-GEIGY 1.9 mg/m 2
  • R01 3,4-dihydroxybenzonitrile
  • R02 3,4-dihydroxybenzophenone
  • S02 tetrachlorophthalic acid anhydride
  • S03 benzotriazole
  • ULTRAVON TM W 75-85% concentrate of a sodium arylsulfonate from Ciba Geigy converted into acid form by passing through an ion exchange column;
  • SYLOID TM 72 a silica from Grace;
  • SERVOXYL TM VPDZ 3/100 a mono[isotridecyl polyglycolether (3 EO)] phosphate, from SERVO DELDEN B.V.;
  • SERVOXYL TM VPAZ 100 a mixture of monolauryl and dilauryl phosphate, from SERVO DELDEN B.V.; MICROACE TAL
  • thermographic recording materials of INVENTION EXAMPLES 1 to 16 and COMPARATIVE EXAMPLES 1 to 4 were prepared by coating a dispersion with the following ingredients in 2-butanone onto a 175 ⁇ m thick blue-pigmented polyethylene terephthalate support with CIELAB a*- and b*- values of -9.5 and -17.9 respectively subbed on the emulsion-coated side with subbing layer 01 giving layers after drying at 50°C for 1h in a drying cupboard with the compositions given in Table 1.
  • Table 1 Comparative example nr.
  • thermosensitive elements were then coated with an aqueous composition with the following ingredients, which was adjusted to a pH of 3.8 with 1N nitric acid, to a wet layer thickness of 85 ⁇ m and then dried at 50°C for 15 minutes to produce a protective layer with the composition:
  • the protective layer was hardened by heating the substantially light-insensitive thermographic recording material at 45°C for 7 days at a relative humidity of 70%.
  • thermographic recording materials of INVENTION EXAMPLES 1 to 16 and COMPARATIVE EXAMPLES 1 to 4 were printed using a DRYSTAR TM 4500 printer from AGFA-GEVAERT with a resolution of 508 dpi which had been modified to operate at a printing speed of 14 mm/s and a line-time of 3.5 ms instead of 7.1 ms and in which the 75 ⁇ m long (in the transport direction) and 50 ⁇ m wide thermal head resistors were power-modulated to produce different image densities.
  • the maximum densities of the images were measured through a visible filter with a MACBETH TM TR924 densitometer.
  • the stainless steel light-box used was 650mm long, 600mm wide and 120mm high with an opening 610mm long and 560mm wide with a rim 10mm wide and 5mm deep round the opening, thereby forming a platform for a 5mm thick plate of white PVC 630mm long and 580mm wide, making the white PVC-plate flush with the top of the light-box and preventing light loss from the light-box other than through the white PVC-plate.
  • This light-box was fitted with 9 Planilux TM TLD 36W/54 fluorescent lamps 27mm in diameter mounted length-wise equidistantly from the two sides, with the lamps positioned equidistantly to one another and the sides over the whole width of the light-box and with the tops of the fluorescent tubes 30mm below the bottom of the white PVC plate and 35mm below the materials being tested.
  • the shifts in CIELAB a*- and b*-values at an optical density, D, of 1.0 and the shift in the CIELAB b*-value were determined for INVENTION EXAMPLES 1 to 16 and COMPARATIVE EXAMPLES 1 to 4 and the results are given in Table 2.
  • Table 2 Comparative Example nr.
  • thermosensitive thermographic recording materials of INVENTION EXAMPLES 1 to 16 in which the thermosensitive elements contain a compound according to formula (I) exhibit substantially improved stability of the b* CIELAB values of the image background to light exposure compared with the substantially light-insensitive thermographic recording material of COMPARATIVE EXAMPLE 1 which is identical to the substantially light-insensitive thermographic recording materials of INVENTION EXAMPLES 1 to 16 except for the absence of a compound according to formula (I) in the thermosensitive element and also compared with the substantially light-insensitive thermographic recording materials of COMPARATIVE EXAMPLES 2 to 4, in which the compounds A01, A02 and A03 are present instead of a stabilizer according to formula (I).
  • the substantially light-insensitive thermographic recording materials of INVENTION EXAMPLE 19 was prepared as described for INVENTION EXAMPLE 3 and INVENTION EXAMPLES 17 and 18 as for INVENTION EXAMPLE 3 except that concentrations of MBIZ-3 of 5 and 8 mol% were used instead of 10 mol% with respect to silver behenate.
  • the substantially light-insensitive thermographic recording materials of INVENTION EXAMPLE 22 was prepared as described for INVENTION EXAMPLE 4 and INVENTION EXAMPLES 20 and 21 as for INVENTION EXAMPLE 4 except that concentrations of MBIZ-4 of 5 and 8 mol% were used instead of 10 mol% with respect to silver behenate.
  • thermosensitive elements of the substantially light-insensitive thermographic recording materials of INVENTION EXAMPLES 17 to 22 together with those for INVENTION EXAMPLES 3 and 4 and COMPARATIVE EXAMPLE 1 in which no additional stabilizer is present in the thermosensitive element are summarized in Table 3 below.
  • Table 3 Comparative example nr. stabilizer AgBeh coverage [g/m 2 ] BL5HP [g/ m 2 ] R01 mol% vs AgB R02 mol% vs AgB T02 mol% vs AgB S01 mol% vs AgB S02 mol% vs AgB VL [g /m 2 ] Oil [g/ m 2 ] type conc.
  • thermographic recording materials of COMPARATIVE EXAMPLES 5 to 8 and INVENTION EXAMPLES 23 to 34 were prepared by coating a dispersion with the following ingredients in 2-butanone onto a 175 ⁇ m thick blue-pigmented polyethylene terephthalate support with CIELAB a*- and b*- values of -9.5 and -17.9 respectively subbed on the emulsion-coated side with subbing layer 01 giving layers after drying at 50°C for 1h in a drying cupboard with the compositions given in Table 5 below.
  • thermosensitive elements were then coated with a protective layer as described for substantially light-insensitive thermographic recording materials of COMPARATIVE EXAMPLES 1 to 4 and INVENTION EXAMPLES 1 to 16.
  • Table 5 Comparative example nr. stabilizer AgBeh coverage [g/m POLY 01 [g/ ] m 2 ] R01 mol% vs AgB R02 mol vs AgB T01 % mol vs AgB T02 % mol vs AgB S01 mol% vs AgB S02 mol vs AgB S03 % mol vs AgB VL % [g /m 2 ] Oil [g/ m 2 ] type conc.
  • thermosensitive elements of the substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLES 5 to 8 and INVENTION EXAMPLES 23 to 34 are significantly different from those of the substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLES 1 to 4 and INVENTION EXAMPLES 1 to 22 in two important respects: they contain benzotriazole (S03) as a further stabilizer and they contain as binder POLY 01, a copolymer of vinyl aceto-acetal, vinyl butyral, vinyl alcohol and vinyl acetate instead of BL5HP, a polyvinyl butyral.
  • Benzotriazole is widely used as a stabilizer in substantially light-insensitive thermographic materials and has excellent stabilizing properties except in respect of shelf-life stability with a strong increase in the b* CIELAB value at density of 1.0.
  • the substantially light-insensitive thermographic materials of INVENTION EXAMPLES 23 to 34 all exhibit substantially higher shelf-life stability i.e. a lower increase in b* CIELAB value at a density of 1.0, than the substantially light-insensitive thermographic material of COMPARATIVE EXAMPLE 5 in which no further stabilizer is present. Therefore, stabilizers according to formula (I) are surprisingly capable of at least ameliorating the poor shelf-life stability of thermographic materials with benzotriazole.
  • thermosensitive elements contained a compound according to formula (I) and the binder used was POLY 01 exhibited a better image tone and image tone stability profile than the substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLES 6 to 8 in which the thermosensitive elements contain one of compounds A01, A02 or A03 in the same molar concentration in respect to silver behenate: higher b* values in prints with fresh film and very poor shelf-life stability in the presence of A01; higher b* values in prints with fresh film and a strong increase in the b* value for Dmin in light box experiments in the presence of A02; and higher a* values in prints with fresh film and a very strong increase in the b* value for Dmin in light box experiments in the presence of A03.
  • thermosensitive thermographic materials of COMPARATIVE EXAMPLES 9 and 10 and INVENTION EXAMPLES 35 to 42 was prepared as described for COMPARATIVE EXAMPLES 5 to 8 and INVENTION EXAMPLES 23 to 34 except as indicated in the thermosensitive element compositions given in Table 7 below.
  • Table 7 Comparative example nr.
  • benzotriazole and the stabilizer according to formula (I) appears to depend upon the choice of stabilizer according to formula (I), being 5 mol% benzotriazole/2 mol% MBIZ-3 in the case of MBIZ-3, being 5 mol% benzotriazole/5 mol% stabilizer according to formula (I) in the case of MBIZ-7, MBIZ-10 and MBIZ-11 and being 5 mol% benzotriazole/2-4 mol% MBIZ-13 in the case of MBIZ-13.

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Claims (9)

  1. Ein wesentlich lichtunempfindliches thermografisches Schwarzweiß-Einzelbogenaufzeichnungsmaterial mit einem Träger und einem wärmeempfindlichen Element, wobei das wärmeempfindliche Element ein wesentlich lichtunempfindliches organisches Silbersalz, ein organisches Reduktionsmittel dafür in thermischer wirksamer Beziehung dazu, zumindest ein Bindemittel und zumindest einen Stabilisator der Formel (I) enthält :
    Figure imgb0038
     in der :
    R1, R2, R3 und R4 unabhängig voneinander jeweils ein Wasserstoffatom, ein Halogenatom oder eine alifatische Gruppe, eine Alkoxygruppe, eine Nitrogruppe, eine Acylgruppe, eine Sulfonylgruppe, eine Nitrilgruppe, eine Alkarylgruppe, eine Arylgruppe, eine Aminogruppe, eine Thioalkylgruppe, eine Aldehydgruppe, eine Harnstoffgruppe, eine -O-(C=O)-Alkylgruppe, eine -O-(C=O)-Arylgruppe, eine -O-(C=O)-O-Alkylgruppe, eine -O-(C=O)-O-Arylgruppe, eine -NH-(C=O)-Alkylgruppe, eine -NH-(C=O)-Arylgruppe, eine -(C=O)-NH-Alkylgruppe, eine -(C=O)-NH-Arylgruppe, eine -NH-(SO2)-Alkylgruppe, eine -NH-(SO2)-Arylgruppe, eine -(SO2)-NH-Alkylgruppe oder eine -(SO2)-NH-Arylgruppe bedeuten,
    X -A(-M)n oder eine gegebenenfalls substituierte alifatische Gruppe, eine gegebenenfalls substituierte cycloalifatische Gruppe oder eine gegebenenfalls substituierte aromatische Gruppe bedeutet, wobei bei jeder dieser Gruppen mindestens eines der Kohlenstoffatome in der Kette oder im Ring durch ein S-Atom, O-Atom, Si-Atom, N-Atom und/oder P-Atom substituiert sein kann,
    n 2, 3 oder 4 bedeutet und
    A eine gegebenenfalls substituierte alifatische Gruppe, eine gegebenenfalls substituierte cycloalifatische Gruppe oder eine gegebenenfalls substituierte aromatische Gruppe bedeutet, wobei bei jeder dieser Gruppen mindestens eines der Kohlenstoffatome in der Kette oder im Ring durch ein S-Atom, O-Atom, Si-Atom, N-Atom und/oder P-Atom substituiert sein kann,
    wobei alle (-M)-Gruppen unabhängig voneinander eine gegebenenfalls substituierte -(2-S-Imidazol)-Gruppe oder eine gegebenenfalls substituierte, mit einem aromatischen Ringsystem anellierte -(2-S-Imidazol)-Gruppe bedeuten, wobei -M durch ein Halogenatom oder eine alifatische Gruppe, eine Alkoxygruppe, eine Nitrogruppe, eine Acylgruppe, eine Sulfonylgruppe, eine Nitrilgruppe, eine Alkarylgruppe oder eine Arylgruppe substituiert sein kann.
  2. Wesentlich lichtunempfindliches thermografisches Schwarzweiß-Einzelbogenaufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass A eine gegebenenfalls substituierte Alkylgruppe, eine gegebenenfalls substituierte Alkenylgruppe, eine gegebenenfalls substituierte Alkynylgruppe, eine gegebenenfalls substituierte Alkyarylgruppe, eine gegebenenfalls substituierte heterocyclische Alkylgruppe, eine gegebenenfalls substituierte heteroaromatische Alkylgruppe, eine gegebenenfalls substituierte Alkylgruppe, in der zumindest eines der nichtendständigen Kohlenstoffatome in der Hauptkette durch ein Sauerstoffatom oder ein Schwefelatom substituiert ist, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Alkyl-Aryl-Alkylgruppe, eine gegebenenfalls substituierte Alkyl-Heteroaryl-Alkylgruppe, eine gegebenenfalls substituierte Alkyl-COO-Alkyl-OOC-Alkylgruppe, eine gegebenenfalls substituierte Alkyl-O-COO-Alkylgruppe, eine gegebenenfalls substituierte Alkyl-CONH-Alkylgruppe oder eine gegebenenfalls substituierte Alkyl-COO-Aryl-OOC-Alkylgruppe bedeutet.
  3. Wesentlich lichtunempfindliches thermografisches Schwarzweiß-Einzelbogenaufzeichnungsmaterial nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass X im zumindest einen Stabilisator gemäß Formel (I) -A-M bedeutet und -M eine -(2-S-Imidazol)-Gruppe oder eine mit einem aromatischen Ringsystem anellierte -(2-S-Imidazol)-Gruppe bedeutet.
  4. Wesentlich lichtunempfindliches thermografisches Schwarzweiß-Einzelbogenaufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass X im zumindest einen Stabilisator gemäß Formel (I) -A-(CH2)m-M bedeutet, wobei m eine Zahl von 2 bis 20 ist und -M eine -(2-S-Imidazol)-Gruppe oder eine mit einem aromatischen Ringsystem anellierte -(2-S-Imidazol)-Gruppe bedeutet.
  5. Wesentlich lichtunempfindliches thermografisches Schwarzweiß-Einzelbogenaufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass X im zumindest einen Stabilisator gemäß Formel (I) -A-(CH2)m-M bedeutet, wobei m eine Zahl von 4 bis 9 ist und -M eine -(2-S-Imidazol)-Gruppe oder eine mit einem aromatischen Ringsystem anellierte -(2-S-Imidazol)-Gruppe bedeutet.
  6. Wesentlich lichtunempfindliches thermografisches Schwarzweiß-Einzelbogenaufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der zumindest eine Stabilisator aus folgender Gruppe gewählt wird :
    Figure imgb0039
    Figure imgb0040
    Figure imgb0041
  7. Wesentlich lichtunempfindliches thermografisches Schwarzweiß-Einzelbogenaufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass der zumindest eine Stabilisator aus folgender Gruppe gewählt wird :
    Figure imgb0042
    Figure imgb0043
  8. Wesentlich lichtunempfindliches thermografisches Schwarzweiß-Einzelbogenaufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das zumindest eine Bindemittel zumindest ein erstes Polymer enthält, das aus Vinylacetoacetal-Monomereinheiten und Monomereinheiten aus der Gruppe bestehend aus Vinylbutyral-, Vinylalkohol-, Vinylacetat-und Itakonsäure-Monomereinheiten besteht, wobei das Gewichtsverhältnis des zumindest einen Bindemittels zum (zu den) lichtunempfindlichen Silbersalz(en) einer Carbonsäure im wärmeempfindlichen Element über 1,5 liegt, und das zumindest eine Bindemittel gegebenenfalls weniger als 40 Gew.-% eines zweiten Polymers, das aus Vinylbutyral-Monomereinheiten und gegebenenfalls Vinylalkohol- und/oder Vinylacetat-Monomereinheiten besteht, enthält.
  9. Wesentlich lichtunempfindliches thermografisches Schwarzweiß-Einzelbogenaufzeichnungsmaterial nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das wärmeempfindliche Element ferner ein gegebenenfalls substituiertes Benztriazol enthält.
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JPH0619568B2 (ja) * 1986-01-10 1994-03-16 富士写真フイルム株式会社 感光材料の製造方法
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JPH0367256A (ja) * 1989-04-30 1991-03-22 Konica Corp 熱現像カラー感光材料
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