EP1435298A2 - Agents d'amélioration du ton pour des matériaux thermographiques et photothermographiques. - Google Patents

Agents d'amélioration du ton pour des matériaux thermographiques et photothermographiques. Download PDF

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Publication number
EP1435298A2
EP1435298A2 EP03104600A EP03104600A EP1435298A2 EP 1435298 A2 EP1435298 A2 EP 1435298A2 EP 03104600 A EP03104600 A EP 03104600A EP 03104600 A EP03104600 A EP 03104600A EP 1435298 A2 EP1435298 A2 EP 1435298A2
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EP
European Patent Office
Prior art keywords
group
alkyl
optionally substituted
heterocyclic
recording material
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.)
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Application number
EP03104600A
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German (de)
English (en)
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EP1435298A3 (fr
Inventor
Ingrid Geuens
Johan Loccufier
Vera Drieghe
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Agfa HealthCare NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Priority to EP03104600A priority Critical patent/EP1435298A3/fr
Publication of EP1435298A2 publication Critical patent/EP1435298A2/fr
Publication of EP1435298A3 publication Critical patent/EP1435298A3/fr
Withdrawn legal-status Critical Current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
    • 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
    • G03C2200/00—Details
    • G03C2200/40—Mercapto compound

Definitions

  • the present invention concerns toning agents for use in 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.
  • US 3,080,254 discloses a typical heat-sensitive copy paper including in the heat-sensitive layer a thermoplastic binder, e.g ethyl cellulose, a water-insoluble silver salt, e.g. silver stearate and an appropriate organic reductor, of which 4-methoxy-1-hydroxy-dihydronaphthalene is a representative.
  • a thermoplastic binder e.g ethyl cellulose
  • a water-insoluble silver salt e.g. silver stearate
  • an appropriate organic reductor of which 4-methoxy-1-hydroxy-dihydronaphthalene is a representative.
  • Localized heating of the sheet in the thermographic reproduction process, or for test purposes by momentary contact with a metal test bar heated to a suitable conversion temperature in the range of about 90-150 °C causes a visible change to occur in the heat-sensitive layer.
  • the initially white or lightly coloured layer is darkened to a brownish appearance at the heated area.
  • thermographic imaging element comprising a substrate having coated on at least one surface thereof a thermographic imaging system comprising at least one layer comprising light-insensitive organic silver salt; reducing agent for silver ion; binder; toner; and a dye which absorbs radiation in the wavelength range of 750-1100 n, wherein said at least one layer comprising said light-insensitive organic silver salt forms an image density greater than about 1.0 when exposed to 0.10 to 2.0 joules/cm 2 of said radiation in 0.20 to 200 microseconds.
  • the thermographic imaging system of Examples 2, 3, 5 and 6 contained barbituric acid in association with known toning agents such as phthalazinone and succinimide.
  • US 3,893,860 discloses in a photothermographic element comprising a support having thereon (I): (a) photographic silver halide in association with (b) a silver salt of a heterocyclic thione, said heterocyclic thione being represented by the formula: wherein R represents atoms completing a 5-member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms, (c) an organic reducing agent for said silver salt of a heterocyclic thione, and (d) a polymeric, synthetic binder and contiguous to (I), at least one polymer layer (II), the improvement wherein said polymer (A) comprising at least 50% by weight of a polymer (A) comprising the repeating units represented by the formulas: wherein: R 1 is hydrogen or alkyl containing 1 to 4 carbon atoms; R 2 is an imidazoyl, N-substituted carbamoyl, 2-pyrrolidinyl, acetoacetoxyethoxycarbon
  • EP-A 0 921 433 also discloses the use of pyrimidine and asymmetric triazines such as 2,4-dihydroxypyrimidine (uracil), 2-hydroxy-4-amino-pyrimidine and azauracil in the thermographic recording element disclosed therein.
  • uracil 2,4-dihydroxypyrimidine
  • 2-hydroxy-4-amino-pyrimidine 2-hydroxy-4-amino-pyrimidine
  • azauracil in the thermographic recording element disclosed therein.
  • thermographic recording element comprising: a support having a pair of opposed surfaces, at least one antistatic layer containing conductive metal oxide particles and at least one thermographic recording layer containing an organic silver salt and a reducing agent on the first surface of the support, and at least two layers on the other surface of the support, wherein the outermost layer of said at least two layers contains a hydrophobic polymer binder and at least one layer of said at least two layers other than said outermost layer contains a matte agent, wherein: said conductive metal oxide particles are acicular particles having a major axis to minor axis ratio of from 3/1 to 50/1, and said thermographic recording element further comprises a nucleating agent.
  • US 6,479,227 also discloses the use of 2,4-dimercaptopyrimidine, pyrimidine and asymmetric triazines such as 2,4-dihydroxypyrimidine (uracil), 2-hydroxy-4-amino-pyrimidine, azauracil, 4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopryimidine, and 2-mercapto-4-methylpyrimidine hydrochloride in the thermographic recording element disclosed therein.
  • 2,4-dihydroxypyrimidine uracil
  • 2-hydroxy-4-amino-pyrimidine azauracil
  • 4-hydroxy-2-mercaptopyrimidine 2-mercaptopyrimidine
  • 2-mercaptopyrimidine 2,6-diamino-2-mercaptopryimidine
  • 2-mercapto-4-methylpyrimidine hydrochloride in the thermographic recording element disclosed therein.
  • US 3,951,660 discloses a photographic radiation sensitive recording material having therein a radiation sensitive composition and at least one layer containing dispersed in a binding agent a substantially non-light sensitive silver salt, a reducing agent for the non-light sensitive silver salt, and a toner compound, the improvement which comprises the toner being a heterocyclic toner compound of the following formula: in which X represents O or N-R 5 ; R 1 , R 2 , R 3 or R 4 represent hydrogen, alkyl, cycloalkyl, alkoxy, alkylthio, hydroxy, dialkylamino or halogen, in addition to which R 1 and R 2 or R 2 and R 3 or R 3 and R 4 can represent the ring members required to complete an anellated aromatic ring, and R 5 represents alkyl.
  • US 3,951,660 discloses 2,4(1 H ,3 H )-quinazolinedione and various 2,4(1 H ,3 H )-quinazolinedione (benzoyleneurea) derivatives substituted at the nitrogen atom in the 1-position i.e. 2-hydroxy-pyrimidine derivatives annelated at the 5,6 positions with a benzene ring: INVENTION EXAMPLES are disclosed in US 3,951,660 in which the use of compounds 1, 3 and 26 as toning agents in thermographic recording materials is exemplified.
  • US-P 3,885,967 discloses a photosensitive material for a thermally developable lightsensitive element which comprises: a) a silver salt component comprising silver laurate or silver caprate, b) a catalytic amount of a photosensitive silver halide component comprising a photosensitive silver halide, or a compound which reacts with silver laurate or silver caprate to form a photosensitive silver halide, c) a reducing agent, d) a binder, and e) a toning agent comprising a compound represented by the formula: wherein R 1 , R 2 , R 3 and R 4 each represents a hydrogen atom, an alkyl group, an aryl group, an acylamido group, a halogen atom, a hydroxyl group or a nitro group.
  • thermography comprising both photothermography and substantially light-insensitive thermography are clearly distinct from that of photography.
  • Photothermographic and substantially light-insensitive thermographic materials differ significantly from conventional silver halide photographic materials which require processing using aqueous processing solutions.
  • thermographic imaging materials In photothermographic and substantially light-insensitive thermographic imaging materials, a visible image is created by heat as a result of the reaction of a developer incorporated within the element. Heat at 50°C or more is essential for this development process and temperatures of over 100°C are routinely required for photothermographic materials and still higher temperatures are routinely required for substantially light-insensitive thermographic materials.
  • conventional wet-processed photographic imaging elements require processing in aqueous processing baths to provide a visible image (e.g., developing and fixing baths) and development is usually performed at more moderate temperatures (e.g., 30° to 50°C) to provide a visible image.
  • photothermographic elements only a small amount of silver halide is used to capture light and a different sort of silver (e.g., silver behenate) is used to generate the image with heat.
  • the silver halide serves as a catalyst for the physical development process involving the non-photosensitive, reducible silver source and the incorporated reducing agent.
  • conventional wet-processed black-and-white photographic materials use only one form of silver (i.e. silver halide) that, upon chemical development, is itself converted into the silver image, or upon physical development requires addition of an external silver source (or other reducible metal ions that form black images upon reduction to the corresponding metal).
  • photothermographic materials require an amount of silver halide per unit area that is only a fraction of that used (as little as one-hundredth) of that used in a conventional wet-processed photographic material.
  • thermothermographic materials all of the "chemistry" for imaging is incorporated within the material itself.
  • such materials include a developer (i.e. a reducing agent for the reducible silver ions) while photographic materials usually do not.
  • a developer i.e. a reducing agent for the reducible silver ions
  • photographic materials usually do not.
  • the developer chemistry is physically separated from the photosensitive silver halide until development is desired.
  • the incorporation of the developer into substantially light-insensitive thermographic and photothermographic materials can lead to the increased formation of various types of "fog” or other undesirable sensitometric side effects. Therefore, much effort has gone into the preparation and manufacture of substantially light-insensitive thermographic and photothermographic materials to minimize these problems during the preparation of the substantially light-insensitive thermographic and photothermographic dispersions as well as during coating, storage, and post-processing handling.
  • the unexposed silver halide generally remains intact after development and the material must be stabilized against further imaging and development.
  • silver halide is removed from conventional photographic materials after solution development to prevent further imaging (i.e. in the aqueous fixing step).
  • the binder is capable of wide variation and a number of binders (both hydrophilic and hydrophobic) are useful.
  • conventional photographic materials are limited almost exclusively to hydrophilic binders such as gelatin.
  • thermographic and substantially light-insensitive thermographic elements require thermal processing, they pose different considerations and present distinctly different problems in manufacture and use, compared to conventional wet-processed silver halide photographic materials.
  • Additives that have one effect in conventional silver halide photographic materials may behave quite differently when incorporated in substantially light-insensitive thermographic or photothermographic materials where the underlying chemistry is significantly more complex.
  • the incorporation of such additives as, for example, stabilizers, antifoggants, speed enhancers, sensitizers, supersensitizers and spectral and chemical sensitizers in conventional photographic materials is not predictive of whether such additives will prove beneficial or detrimental in substantially light-insensitive thermographic or photothermographic materials.
  • a photographic antifoggant useful in conventional photographic materials to cause various types of fog when incorporated into substantially light-insensitive thermographic or photothermographic materials, or for supersensitizers that are effective in photographic materials to be inactive in photothermographic materials.
  • thermographic materials are described in Imaging Processes and Materials (Neblette's Eighth Edition); J. Sturge et al, Ed; Van Nostrand Rheinhold: New York, 1989; Chapter 9 and in Unconventional Imaging processes; E. Brinckman et al., Ed: The focal Press: London and New York: 1978: pp. 74-75, and in Zou, Sahyun, Levy and Serpone, J. Imaging Sci. Technol. 1996, 40, pp. 94-103.
  • 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.
  • Thermographic and photothermographic materials with prior art toning agents exhibit poor storage properties, as is the case with e.g. phthalazinone, and/or an image colour which has an insufficiently neutral tone for black and white images, as is the case with e.g. succinimide, phthalimide, phthalic acid and phthalazine.
  • thermographic materials as disclosed in US-P 3,951,660, represented an improvement in storage properties and in the neutrality of the image tone, whether substituted, as disclosed in US-P 3,885,967 and US-P 3,951,660, or unsubstituted, as disclosed in US-P 3,951,660.
  • Such toning agents are insufficiently soluble in ecologically acceptable coating solvents and thermographic materials containing these toning agents exhibit a undesirably strong deterioration in image colour and an undesirable increase in image background (fog) upon storage.
  • thermographic materials diffuse through the thermographic materials to the thermal head resulting in cloudiness in the imaging material, deposits of ingredients and by-products from the image-forming process on the surface of the thermographic material and, in the case of substantially light-insensitive thermographic materials in thermal head printers, image degradation due to thermal head contamination.
  • thermographic recording materials suitable for use in thermographic printers without adverse effect on the image tone.
  • thermographic materials which adsorb particularly rapidly on silver nano-particles as demonstrated by time-resolved SERS measurements and bring about rapid aggregation thereof render the image tone of thermographic materials more neutral in thermographic materials, whose image forming process is based upon the image-wise reduction of substantially light-insensitive organic silver salts, i.e. exhibit so-called toning properties.
  • thermographic materials a combination of toning agents both exhibiting rapid adsorption on silver nano-particles and capable of bringing about rapid aggregation thereof, but exhibiting slow and fast diffusion respectively in the particular polymer matrix, exhibit favourable synergistic effects with respect to image tone and diffusion thereof to the surface of the thermographic materials.
  • a black and white monosheet thermographic recording material comprising a support and a thermosensitive element, the thermosensitive element containing a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith, a binder and at least one toning agent, characterized in that the at least one toning agent is represented by formula (I): wherein R 1 is a hydrogen atom or an alkyl, an alkenyl, an alkynyl, a cycloalkyl, an alkaryl, an aryl, a heterocyclic or a heteroaryl group all of which may be optionally substituted; R 2 and R 3 are independently a hydrogen or a halogen atom or an amino, amide, ester, carboxy, carbonato, alkyl, alkenyl, alkynyl, cycloalkyl, alkaryl, aryl, heterocyclic or heteroaryl group all of which may be optionally substituted; R 2 and R 3
  • thermographic material as used in disclosing the present invention includes both photothermographic materials and substantially light-insensitive thermographic materials.
  • 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.
  • carbocyclic ring includes both alicylic rings and aromatic rings.
  • Substantially light-insensitive means not intentionally light sensitive.
  • 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 and have been used to characterize the image tone of thermographic materials of the present invention.
  • substantially water-free condition means heating at a temperature of 80 to 250°C.
  • substantially water-free condition means that the reaction system is approximately in equilibrium with water in the air, and water for inducing or promoting the reaction is not particularly or positively supplied from the exterior to the element. Such a condition is described in T.H. James, "The Theory of the Photographic Process", Fourth Edition, Macmillan 1977, page 374.
  • 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 a 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.
  • Such materials include 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 herein incorporated by reference.
  • thermosensitive element containing a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith, a binder and at least one toning agent, characterized in that the at least one toning agent is a compound represented by formula (I).
  • R 1 is an alkyl, an alkenyl, an alkynyl, a cycloalkyl, an alkaryl, an aryl, a heterocyclic or a heteroaryl group all of which may be optionally substituted.
  • the compound according to formula (I) is represented by formula (II): wherein R 1 is a hydrogen atom or an alkyl, an alkenyl, an alkynyl, a cycloalkyl, an alkaryl, an aryl, a heterocyclic or a heteroaryl group all of which may be optionally substituted; R 2 and R 3 are independently a hydrogen or a halogen atom or an amino, amide, ester, carboxy, carbonato, alkyl, alkenyl, alkynyl, cycloalkyl, alkaryl, aryl, heterocyclic or heteroaryl group all of which may be optionally substituted; R 2 and R 3 may together represent the atoms necessary to complete a heteroaromatic ring with no more than one nitrogen atom, an alicyclic ring or a heterocyclic ring which all may be optionally substituted; and with the provis
  • the 2-hydroxy-pyrimidine derivative is selected from the group consisting of 2-hydroxy-pyrimidines annelated with a heterocyclic ring, 2-hydroxy-pyrimidine derivatives annelated with a carbocyclic ring including purine derivatives.
  • the substituent for R 1 is selected from the group consisting of alkyl, aryl, alkoxy, hydroxy, carboxy, ester, amide, sulfo and sulfoalkyl groups.
  • the substituent for R 2 is selected from the group consisting of alkyl, aryl, alkoxy, hydroxy, carboxy, ester, amide, sulfo and sulfoalkyl groups.
  • the substituent for R 3 is selected from the group consisting of alkyl, aryl, alkoxy, hydroxy, carboxy, ester, amide, sulfo and sulfoalkyl groups.
  • the compound according to formula (I) is selected from the group consisting of: xanthine (2,6-dihydroxy-purine), xanthine derivatives and 2,6,8-trihydroxy-purine (uric acid).
  • the compound according to formula (I) is selected from the group consisting of
  • Suitable compounds according to formula (I), according to the present invention include:
  • the thermosensitive element further contains at least one toning agent selected from the group consisting of compounds according to formula (III), wherein R 5 is an alkyl group optionally substituted with a hydroxy, carboxy, carboxy ester, acyl or carbonato group; X is S, O or N-R 10 ; R 6 is an optionally substituted alkyl group; R 6 , R 7 , R 8 and R 9 independently represent a hydrogen atom, a halogen atom or an alkyl, an alkoxy, a thio-alkoxy, a nitro, a cyano, a carboxy, a carboxy ester, an acyl, an aldehyde, an acylamido, a sulphonamido, an acylamino, a carbonato, a hydroxy or an aryl group or at least one of R 6 and R 7 , R 7 and R 8
  • Suitable co-toning agents according to formula (I) are:
  • Suitable co-toning agents represented by formula (II) according to the present invention include:
  • Suitable benzoxazine dione co-toning agents are:
  • a further toning agent such as benzoxazine dione, a benzoxazine dione derivative, phthalazinone, a phthalazinone derivative, pyridazone or a pyridazone derivative
  • the thermosensitive element contains at least two toning agents with a diffusion in the binder differing by at least a factor of 2, but less than a factor of 1000 and preferably by at least a factor of 10.
  • the thermosensitive element further contains at least one toning agent selected from the group consisting of 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, 7-butoxy-benzo[e][1,3]oxazine-2,4-dione, 7-(ethylcarbonato)-benzo[e][1,3]oxazine-2,4-dione,
  • 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-dihydroxy-benzene 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 and 3,4-dihydroxy-benzoic acid esters are preferred, with those described in EP-A 0 692 733, EP-A 0 903 625, EP-A 1 245 403 and EP-A 1 245 404 herein incorporated by reference being particularly preferred e.g.
  • 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
  • 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 further contains a stabilizer.
  • the thermosensitive element further contains a stabilizer selected from the group consisting of benzotriazole; substituted benzotriazoles; aromatic polycarboxylic acid, such as ortho-phthalic acid, 3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid, pyromellitic acid and trimellitic acid and anhydrides thereof; 1-phenyl-5-mercaptotetrazole compounds in which the phenyl group is substituted with a substituent containing an optionally substituted aryl group, 1-(5-mercapto-1-tetrazolyl)-acetyl compounds represented by formula (V): wherein R 3 is -NR 4 R 5 , -OR 6 or an optionally substituted aryl or heteroaryl group; R 4 is hydrogen or an optionally substituted alkyl, aryl or heteroaryl group; R 5 is an optionally substituted aryl or heteroaryl
  • the thermosensitive element further contains at least one optionally substituted aliphatic or carbocyclic 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 used in anhydride form or partially esterified on the condition that at least two free carboxylic acids remain or are available during the heat recording step.
  • thermosensitive element further contains photosensitive silver halide, thereby rendering the thermographic material photothermographic.
  • the photosensitive silver halide used in the present invention may be employed in a range of 0.1 to 100 mol percent; preferably, from 0.2 to 80 mol percent; particularly preferably from 0.3 to 50 mol percent; especially preferably from 0.5 to 35 mol %; and especially from 1 to 12 mol % 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 chemically sensitized with a chemical sensitising merocyanine dye containing a thione group, and optionally 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. in addition to sensitization with specific reducing agents, according to the present invention.
  • 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.
  • the grain size of the silver halide particles can be determined by the Moeller Teller method in which the sample containing silver halide particles is sedimented upon a filter paper, which is submerged in electrolyte together with a negative platinum needle-shaped electrode and a reference electrode. The silver halide particles on the filter paper are slowly scanned individually with the needle-shaped electrode, whereupon the silver halide grains are individually electrochemically reduced at the cathode. This electrochemical reduction is accompanied by a current pulse, which is registered as a function of time and integrated to give the charge transfer Q for the electrochemical reduction of the silver halide particle, which is proportional to its volume. From their volume the equivalent circular grain diameter of each grain can be determined and therefrom the average particle size and size distribution.
  • 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.
  • 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 material preferably containing an infra-red absorbing compound, or by direct thermal imaging with a thermal head.
  • 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.
  • 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.
  • Photothermographic recording 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 focused light source, such as a CRT light source; a UV, visible or IR wavelength laser, such as a Violet-laser, a He/Ne-laser or an IR-laser diode, e.g. emitting at 400nm, 630nm, 650nm, 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.
  • a finely focused light source such as a CRT light source
  • a UV, visible or IR wavelength laser such as a Violet-laser, a He/Ne-laser or an IR-laser diode, e.g. emitting at 400nm, 630
  • 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.
  • 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.
  • isobutylurea prepared from potassium cyanate and isobutylamine by refluxing the mixture at pH 4 to 5 for 1 hour
  • 12.7 g (0.149 mol) cyanoacetic acid were dissolved in 39 mL acetic anhydride and heated to 80°C for 2 hours. After cooling the mixture was treated with 70 mL diethylether, then cooled to 0°C whereupon 1-cyanoacetyl-3-isobutylurea precipitates out.
  • Subbing layer Nr. 01 on the emulsion side of the support had the composition: 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
  • thermosensitive element Ingredients in the thermosensitive element in addition to the above-mentioned ingredients:
  • a screening method was developed using a silver hydrosol, which was prepared 20 to 30 minutes before the compound TA-1 was screened. 1 mL of a 0.001M solution of the compound being screened was then added to 10 mL of this yellow silver hydrosol. If the silver hydrosol changed colour within one hour, 10 mL of a 0.5% aqueous gelatin solution was added 10s after this change of colour to prevent further silver aggregation. If no change in colour was observed after 1 hour, the concentration of the compound being screened in the hydrosol was increased from 10 -4 M to 10 -3 M. Control experiments were carried out with each batch of silver hydrosol to check its performance with a 10 -3 M solution of BOD06, a compound giving immediate aggregation.
  • the degrees of aggregation obtained with TA-1 is given in Table 1A below and the degrees of aggregation for BOD01 to BOD05 are given in Table 1B below.
  • the diffusion experiments were carried out with the surface of a 15g/m 2 layer of S-LEC BL5HP containing the compound being screened in a concentration of 15 mol% with respect to a quantity of silver behenate a quarter of that of the S-LEC BL5HP coverage coated on a glass support in contact with the surface of a 10g/m 2 layer of S-LEC BL5HP containing glutaric acid in a concentration of 24 mol% with respect to a quantity of silver behenate a quarter of that of the S-LEC BL5HP coverage coated on a SERS-probe. In this configuration the SERS-probe was uppermost.
  • the diffusion experiment was carried out by heating the S-LEC BL5HP-coated glass support with the glass support in contact with an electrically heated plate at a temperature of 150°C for a predetermined time. The configuration was then removed from the heated plate and a Raman spectrum was taken by Dilor XY-laser spectroscopy with the 514 nm line of a Coherent Innova 70C argon/krypton mixed gas laser at 12mW through the glass plate to ascertain whether the ingredient being screened had diffused to the silver nano-particles in the SERS-probe on the basis of its surface-enhanced Raman spectrum due to contact with silver using the so-called "Surface Enhanced Raman Scattering" (SERS)-effect.
  • SERS Surface Enhanced Raman Scattering
  • coated glass support and the coated SERS-probe were prepared by coating the glass support and SERS-probe respectively with a 2-butanone solution of S-LEC BL5HP and the ingredient being screened and glutaric acid respectively, drying at room temperature and finally heating the coated glass support and the coated SERS-probe for 10 minutes at 85°C.
  • the SERS-probe was prepared by adding an aqueous solution of silver nitrate to an aqueous solution of potassium borohydride and stabilizing the 5 to 10 nm silver nuclei by adding polyvinyl alcohol, the final composition being 0.01M in silver nitrate, 0.015M in potassium borohydride and 1% in polyvinyl alcohol.
  • the resulting silver hydrosol was then added to a solution of gelatin containing a hardener, a biocide, an inorganic pigment and a hardening regulator.
  • the resulting mixture was coated to a dry thickness of 100 nm onto glass plates giving a thin, yellow transparent film containing silver nuclei 5 to 10 nm in diameter.
  • the coated glass plate was then immersed in deionised water at 40°C for 15 minutes and then in a 0.001M aqueous solution of silver nitrate containing 0.5% of gelatin and 0.001M in ascorbic acid, a reducing agent for silver cations, at 25°C. Electroless deposition of silver occurred on the silver nuclei rather than nucleation of new particle, because nucleation requires much more energy than growth of the silver nuclei already present. Finally the layer containing 90 nm silver particles was rinsed with deionised water and dried. These 90nm silver particles were required for the laser wavelength used in these experiments (514.5 nm). Other silver particle sizes can be obtained, depending upon the composition of the bath, its temperature and the time of immersion.
  • TA-1 produced a degree of silver particle aggregation of +++ within 10s and exhibited a diffusion time at 150°C through S-LEC BL5HP in the presence of glutaric acid of 120s.
  • thermographic materials of COMPARATIVE EXAMPLES 6 to 13 and INVENTION EXAMPLES 2 to 6 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 85°C for 3 minutes in a drying cupboard with the compositions given in Table 2 below.
  • 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: ERCOLTM 48 20 2.1g/m 2 LEVASILTM VP AC 4055 1.05g/m 2 ULTRAVONTM W 0.075g/m 2 SYLOIDTM 72 0.09 g/m 2 SERVOXYL
  • thermographic recording materials of COMPARATIVE EXAMPLES 6 to 13 and INVENTION EXAMPLES 2 to 6 were printed using a DRYSTARTM 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.
  • Table 7 show that a combinations of two benzoxazine dione toning agents does not exhibit the synergetic more negative a* and b* CIELAB values or the synergetic reduction in diffusion exhibited by a combination of a toning agent, according to the present invention, and a benzoxazine dione toning agent.
  • the results in Table 8 show that toning agents, according to the present invention, exhibit in a particular thermosensitive element a marginally more neutral a* CIELAB-value.
  • the a* CIELAB-value observed is strongly dependent upon the ingredients used in the substantially light-insensitive thermographic material, which means that with other ingredients a similar difference in a* CIELAB-value would mean the difference between tone neutrality i.e. an a* CIELAB value in the neighbourhood of 0 and a strongly reddish image tone i.e. a strongly positive a* CIELAB-value.
  • thermographic materials of COMPARATIVE EXAMPLES 14 to 18 and INVENTION EXAMPLES 7 to 20 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 85°C for 3 minutes in a drying cupboard with the compositions given in Table 9 below.
  • thermographic recording materials of COMPARATIVE EXAMPLES 14 to 18 and INVENTION EXAMPLES 7 to 20 as described for the thermographic recording materials of COMPARATIVE EXAMPLE 6 to 13 and INVENTION EXAMPLES 2 to 6 and the image tone of fresh prints assessed as for the thermographic recording materials of COMPARATIVE EXAMPLE 6 to 13 and INVENTION EXAMPLES 2 to 6.
  • the results are given in Tables 10 and 11. Comparative Example Nr.
  • thermographic recording materials of INVENTION EXAMPLES 7 to 19 were all more blue and hence more acceptable for a radiologist viewing images in transmission than those of the thermographic recording materials of COMPARATIVE EXAMPLES 14 to 16 and 18.
  • toning agents TA-1, TA-3 to TA-12, TA 15 and TA-16 exhibit more favourable image toning properties as indicated by the less positive a*- and b*-values of the corresponding thermographic recording materials compared with those of the thermographic recording material of COMPARATIVE EXAMPLE 17 which does not contain a toning agent.

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  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP03104600A 2002-12-19 2003-12-09 Agents d'amélioration du ton pour des matériaux thermographiques et photothermographiques. Withdrawn EP1435298A3 (fr)

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EP02102832 2002-12-19
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4030930A (en) * 1974-02-15 1977-06-21 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive material
US6146823A (en) * 1998-04-08 2000-11-14 Fuji Photo Film Co., Ltd Thermographic image-recording element
US20020012888A1 (en) * 2000-06-15 2002-01-31 Yasunori Wada Photothermographic material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5288329A (en) * 1976-01-20 1977-07-23 Fuji Photo Film Co Ltd Image receiving material
JPH11102047A (ja) * 1997-09-26 1999-04-13 Fuji Photo Film Co Ltd 熱現像画像形成材料
JP2000314939A (ja) * 1999-04-30 2000-11-14 Fuji Photo Film Co Ltd 熱現像感光材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4030930A (en) * 1974-02-15 1977-06-21 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive material
US6146823A (en) * 1998-04-08 2000-11-14 Fuji Photo Film Co., Ltd Thermographic image-recording element
US20020012888A1 (en) * 2000-06-15 2002-01-31 Yasunori Wada Photothermographic material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 197736 Derwent Publications Ltd., London, GB; Class E13, AN 1977-63652Y XP002279437 -& JP 52 088329 A (FUJI PHOTO FILM CO LTD) 23 July 1977 (1977-07-23) *
DATABASE WPI Section Ch, Week 199925 Derwent Publications Ltd., London, GB; Class E13, AN 1999-297998 XP002279438 -& JP 11 102047 A (FUJI PHOTO FILM CO LTD) 13 April 1999 (1999-04-13) *
DATABASE WPI Section Ch, Week 200119 Derwent Publications Ltd., London, GB; Class E19, AN 2001-184959 XP002279436 -& JP 2000 314939 A (FUJI PHOTO FILM CO LTD) 14 November 2000 (2000-11-14) *

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