EP0227141A1 - Verfahren zur Herstellung eines photothermographischen Materials - Google Patents

Verfahren zur Herstellung eines photothermographischen Materials Download PDF

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Publication number
EP0227141A1
EP0227141A1 EP86202055A EP86202055A EP0227141A1 EP 0227141 A1 EP0227141 A1 EP 0227141A1 EP 86202055 A EP86202055 A EP 86202055A EP 86202055 A EP86202055 A EP 86202055A EP 0227141 A1 EP0227141 A1 EP 0227141A1
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EP
European Patent Office
Prior art keywords
silver
micelles
core
silver halide
halide
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.)
Withdrawn
Application number
EP86202055A
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English (en)
French (fr)
Inventor
Luc Herwig Leenders
Frans Carl De Schryver
Erwin Quanten
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
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Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Publication of EP0227141A1 publication Critical patent/EP0227141A1/de
Withdrawn legal-status Critical Current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

Definitions

  • the present invention relates to a photothermographic recording material and process for the production thereof.
  • a photothermographic recording material is a light-sensitive material that can be processed by application of heat to form a visible image after its image-wise exposure to light.
  • a dry imaging process based on the use of silver halide as photosensitive substance is described e.g. in GB-P 1,110,046 and operates with an imaging layer having the following two main components :
  • the components (a) and (b) must be in catalytic proximity which means that the photolytic silver from the silver halide must be capable to catalyse the image-forming redox-reaction between the silver soap and the reducing agent while heating the recording layer for a few seconds to approximately 100°C so that hereby a silver image develops.
  • a good light-sensitivity is attained when the necessary silver halide is formed in situ at the surface of the non-light-sensitive silver salt by reaction with a compound yielding halide ions, e.g. as described in US-P 3,457,075 and 3,770,448.
  • a material obtained that way has a sensitivity in the short wave region of the visible spectrum in accordance with the inherent sensitivity of the silver halides formed and can be spectrally sensitized to light of longer wavelengths by the addition of spectral sensitizing dyes.
  • the formation in situ of silver halide proceeds with hydrogen bromide as a source of halide ions in equal volumes of alcohol and water wherein a silver soap is dispersed.
  • the dispersion is mixed thoroughly by stirring whereby the silver halide is formed in situ, i.e. in reactive association with the other components needed for the photothermographic image formation.
  • a first coating is made of silver soap, e.g. silver stearate, in a binder such as polyvinyl butyral from a mixture of non polar solvent such as toluene and a polar solvent such as acetone and a second coating is applied thereon containing ammonium bromide, hydroquinone, spectral sensitizing agent and polyvinyl pyrrolidone from acetone.
  • the ammonium bromide amounts to approximately four molar percent of silver stearate.
  • the silver halide is produced in situ in the recording layer by treating the non-­lightsensitive silver salts at their surface with vapours of hydrohalic acids, e.g. hydrogen chloride in the vapour phase.
  • hydrohalic acids e.g. hydrogen chloride
  • the micelles of organic surfactant molecules in non polar solvents have the inverse structure of surfactant micelles in aqueous solutions.
  • micelles In aqueous surfactant solutions micelles have a hydrocarbon core, but in non polar organic solvents inverted micelles have a dense polar core containing water at the center of the micelle.
  • a process for the production of a photothermographic material comprises the steps of
  • a hydrophilic colloid e.g. gelatin, is introduced into the core of said micelles.
  • said photosensitive layer is applied in association with a sub coat and/or top coat containing a developing agent capable of diffusing on heating into the photosensitive layer.
  • Surfactants are amphiphatic substances characterized by a relatively large non polar hydrophobic molecule part carrying chemically linked thereto a polar hydrophilic molecule part, whereby said substances have the property of lowering the surface tension of water.
  • Surfactants suited for use in the production of inverted micelles are either cationic, anionic or non-ionic surfactants.
  • cationic surfactants the ion containing the organic part of the molecule is a cation.
  • cationic surfactants are : alkylammonium salts and salts of higher molecular weight amines.
  • anionic surfactants the ion containing the organic part of the molecule is an anion.
  • anionic surfactants are : higher carboxylic acid metal soaps, sulphosuccinates, higher alkyl sulphonates and alkylaryl sulphonates.
  • non-ionic surfactants are alkyl or alkylaryl substituted polyoxyalkylene compounds such as isooctylphenyl polyoxyethylene ethers.
  • Preferred surfactants for the formation of inverted micelles with relatively large capacity to include an aqueous liquid in their core are amphiphiles having two separate hydrocarbon chains or one branched hydrocarbon chain linked to the ionic structural part.
  • Examples of such surfactants are : the sodium salts of C6-C18 alkyl diesters of phosphoric acid, mono(2-hexyl-decyl) phosphoric acid ester and di-(2-­ethylhexyl)-sulphosuccinic acid.
  • Particularly suited for including a high amount of aqueous liquid are further amphiphiles having an ionic part of the betaine type as e.g. in amino-carboxylic acids such as R-NH-­(CH2) n -COOH, wherein R is C12-C18 alkyl and n is 1 to 4.
  • a cationic surfactant having a halide counter ion is dispersed in the presence of a minute amount of water in an non polar solvent, e.g. an aliphatic, cycloaliphatic or aromatic hydrocarbon liquid or mixtures thereof, to form inverted micelles and a minor amount of water containing a dissolved silver salt, e.g. silver nitrate, is mixed therewith and at least partly introduced into the core of said micelles to obtain the formation of silver halide inside said core.
  • an non polar solvent e.g. an aliphatic, cycloaliphatic or aromatic hydrocarbon liquid or mixtures thereof
  • an anionic surfactant having a silver counter ion is dispersed in the presence of a minute amount of water in a non polar solvent, e.g. an aliphatic, cycloaliphatic or aromatic hydrocarbon liquid or mixtures thereof, to form inverted micelles and a minor amount of water containing a dissolved halide salt, e.g. sodium chloride, is mixed therewith and at least partly introduced into the core of said micelles to obtain the formation of silver halide inside said core.
  • a non polar solvent e.g. an aliphatic, cycloaliphatic or aromatic hydrocarbon liquid or mixtures thereof
  • inverted micelles are formed by dispersing a surfactant in the presence of a minor amount of water containing a water-soluble silver salt, e.g. silver nitrate, in a non polar solvent, and a minor amount of water containing a dissolved halide, e.g. ammonium bromide, is mixed therewith whereby at least a part of the aqueous solution of the halide salt becomes introduced into said cores and the formation of silver halide occurs inside said cores.
  • a surfactant in the presence of a minor amount of water containing a water-soluble silver salt, e.g. silver nitrate, in a non polar solvent
  • a minor amount of water containing a dissolved halide e.g. ammonium bromide
  • inverted micelles are formed by dispersing a surfactant in the presence of a minor amount of water containing a water-soluble halide salt, e.g. sodium chloride, in a non polar solvent, and a minor amount of water containing a dissolved silver salt, e.g. silver nitrate, is mixed therewith whereby the aqueous solution of the silver salt becomes at least partly introduced into said cores and the formation of silver halide occurs inside said cores.
  • a water-soluble halide salt e.g. sodium chloride
  • a first group of inverted micelles is formed by dispersing a surfactant in the presence of a minor amount of water containing a water-soluble silver salt, e.g. silver nitrate, in a non polar solvent
  • a second group of inverted micelles is formed by dispersing a surfactant in the presence of a minor amount of water containing a water-soluble halide salt, e.g. ammonium bromide, in said non polar solvent
  • said both groups of micelles are mixed so that the aqueous contents of the cores become intermixed and the formation of silver halide occurs inside said cores.
  • the inverted micelles are formed by mixing simultaneously in a non polar liquid medium in the presence of a minor amount of water a cationic surfactant having an halide, e.g. chloride, as counter anion and an anionic surfactant having a silver ion as counter cation.
  • a cationic surfactant having an halide e.g. chloride
  • Amounts of lightsensitive silver halide of 1 to 30 % with respect to the the non-lightsensitive silver salt will suffice to form catalytically active silver in the thermal reduction process.
  • Organic silver salts that are substantially insensitive to light and that are used in the present photothermographic material as substances yielding image-silver are preferably silver salt surfactants forming the inverted micelles having inside their cores photosensitive silver halide, but silver sulphonates with higher alkyl (C12-C22) groups and silver salts of aliphatic carboxylic acids known as fatty acids, so-called silver soaps that preferably contain at least 12 carbon atoms, for example silver behenate and silver stearate may be used in addition thereto although they have to be applied in dispersed form because these salts are inherently insoluble in non polar liquids such as n-heptane.
  • silver behenate and silver stearate may be used in the presence of free fatty acid, e.g. behenic acid, which means that the recording composition of photothermographic materials need not to be alkaline to become developable.
  • free fatty acid e.g. behenic acid
  • Other non-lightsensitive silver compounds for use in thermographic recording materials are described in GB-P 1,111,492.
  • the non-lightsensitive silver salts for use according to the present invention have preferably a relatively low melting point, preferably lower than 100°C, to become intimately mixed on heating with the silver nuclei that are formed by the reduction of the silver halide inside the inverted micelles.
  • a relatively low melting point preferably lower than 100°C
  • the inverted micelles will desaggregate and catalytic contact of the photo-exposed silver halide with the non-­photosenstive silver compound yielding the major part of the image silver will be made.
  • an anionic surfactant containing silver counter ions is used in such amounts that it does not only serves for yielding sufficient silver ions in the formation of minute amounts of photosensitive silver halide inside the cores of the inverted micelles but also provides the necessary quantity of silver ions for an image-forming thermal development following the image-wise exposure of the photothermographic material.
  • a particularly suitable anionic surfactant for that purpose is the silver salt of di-(2-ethylhexyl)-sulphosuccinic acid which forms inverted micelles in a non polar solvent such as n-pentane, n-hexane, n-­heptane, n-octane, n-nonane, benzene, cyclohexane, carbon tetrachloride and 2,2-dimethylbutane.
  • Other sulphonates that form inverted micelles in non polar solvents e.g. in n-heptane, are tripentylmethylbenzene sulphonate and dinonylnaphthalene sulphonates. The latter forms smaller micelles in benzene than in n-decane.
  • the preparation of the silver salt of di-(2-ethylhexyl)-sulphosuccinic acid proceeded e.g. as follows : 13.3 g (30 mmole) of sodium di-(2-ethylhexyl)-sulphosuccinate were dissolved in 900 ml of distilled water by stirring vigorously. To the obtained solution a solution of 10.2 g (60 mmole) of silver nitrate in 20 ml of water were added while maintaining said stirring. The solution became slightly opalescent. Stirring was continued for 4 h at 20 °C. Thereupon the aqueous liquid was extracted with diethyl ether, once with 200 ml and thrice with 100 ml.
  • the preparation of silver di-(2-ethylhexyl)-sulphosuccinate may proceed likewise in an analogous way to the preparation of silver salts of fatty acids described in US-P 3,700,458.
  • Reducing agents acting as developing agents for photo-exposed silver halide in a thermographic recording material according to the present invention are e.g. hydroquinone and derivatives thereof which in order to counteract their oxidation by oxygen of the air are preferably used in an acidic medium.
  • Preferred developing agents withstanding better aerial oxidation are o-alkyl-substituted phenols, aminophenols and methoxy-naphthol and derivatives thereof.
  • suitable o-alkyl-­substituted bisphenols as reducing agents for photothermographic recording materials are described in the published German Patent Application (DE-OS) 2,321,328 and US-P 3,679,414, 3,589,903 and 3,589,901.
  • Still other reducing agents for use in photothermographic recording materials are described in Research Disclosure June 1978, item 17029.
  • ingredients that are useful in the image-formation on thermal processing are e.g. substances liberating alkali on heating, so-called alkali-precursors. Representatives thereof are described in the last mentioned Research Disclosure. Particularly useful for liberating alkali by thermal decarboxylation is guanidinium trichloroacetate.
  • Other such precursors are, e.g. urea and the silylamines described in GB-P 1,141,591 yielding ammonia on heating above 80°C and/or co-­crystal adducts of bisphenols and amines as described e.g. in US-P 3, 076,707 liberating an amine on heating.
  • Still other useful ingredients are image tone modifiers (toning agents) and chemical and spectral sensitizers.
  • thermographic recording layer may in order to improve the photographic speed contain pigments that are n-type photoconductors.
  • pigments are, e.g. titanium dioxide and photoconductive zinc oxide prepared by the reduction of zinc vapour (French process).
  • the use of zinc oxide in thermographic recording materials is described e.g. in US-­P 3,457,075.
  • any suitable chemical and/ spectral sensitizing agent known in silver halide photography may be used, which agents in order to come into contact with the silver halide are incorporated into the aqueous medium in the core of the inverted micelles.
  • Toning agents that are preferably used in a thermographic recording material according to the present invention are phthalazinone derivatives as described e.g. in GB-P 1,420,815.
  • the above inverted micelles are incorporated in an appropriate film forming binder that is soluble in the non polar solvent in which the formation of the micelles took place.
  • Suitable film forming binding agents that are soluble in aliphatic or cycloaliphatic hydrocarbon liquids are e.g.
  • the support used in a photothermographic recording material according to the present invention may be a paper or resin film support, e.g. of the type described in Research Disclosure June 1978, item 17029.
  • paper and film supports with glass transition temperature above 190°C are preferred other materials that can withstand processing temperatures, e.g. in the range of 80 to 150°C, may be used likewise, e.g. glass and metal supports.
  • the photothermographic recording layer may be coated with an overcoat layer to make it less susceptible to finger print marks and scratches that may occur in the heat processing.
  • Suitable overcoat layers are described likewise in the already mentioned Research Disclosure wherein also a number of ingredients for colour developing photothermographic recording materials has been disclosed. Suitable ingredients for the production of colour images are e.g. colour couplers that will react with oxidized reducing or developing agent or are leuco dyes that become imagewise oxidized on thermal processing.
  • thermographic recording material For the manufacturing of a thermographic recording material according to the present invention the following compositions A, B, C, and D were prepared.
  • Composition A 0.618 g (0.006 mole) of sodium bromide in 10 ml of distilled water.
  • Composition B 5 g of copolymer of isobutylmethacrylate, stearylmethacrylate, methacrylic acid (75/24.8/0.2 %) dissolved in 50 ml of n-heptane by sonication (ultra-sound treatment).
  • Composition C 0.55 g (0.005 mole) of hydroquinone were dissolved in 10 ml of distilled water.
  • composition D 6.6 g of silver (di-2-ethylhexyl) sulphosuccinate (prepared as described herein) were dissolved in 50 ml of composition B by sonication.
  • composition D For preparing a photothermographic film 2.5 ml of composition D were added to a sufficient amount of composition B to obtain a total volume of 5 ml. Thereupon 50 microliter of composition C were added and mixed by sonication. After that mixing step 130 microliter of composition A were added and sonication was continued till the obtaining of a white turbid dispersion. The thus obtained mixture was coated onto a polyethylene terephthalate support at a wet coating thickness of 200 ⁇ m and dried at the atmosphere to remove the n-heptane.
  • the dried photothermographic layer had a total silver compound content corresponding with 0.88 g of silver per m2, and more particularly contained per m2 0.280 g of AgBr, 3 g of water and 8.3 g of the copolymer of composition C.
  • the dried film was exposed during 5 min through a half-tone pattern using 360 nm light of a UV lamp applied in chromatography, treated for 1 min with ammonia vapour and heated for 5 min at 100 °C.
  • the density (D) obtained in the exposed area was 0.8.
  • Example 1 was repeated with the difference however, that the hydroquinone was replaced by bis(4-hydroxyphenyl)-2,2′-propane (bisphenol A).
  • the film material was prepared and exposed as described in Example 1.
  • the density (D) obtained in the exposed area was 0.510.
  • the thus obtained mixture was coated onto a polyethylene terephthalate support at a wet coating thickness of 200 um and dried at the atmosphere to remove the n-heptane.
  • the dried photothermographic layer contained per m2 0.280 g of AgBr, 3 g of water and 8.3 g of the copolymer of composition C.
  • the dried film was exposed as described in Example 1 and treated for 1 min with ammonia vapour and heated for 5 min at 100 °C.
  • the density (D) obtained in the exposed area was 2.5.
  • the thus obtained dispersion was coated onto a polyethylene terephthalate support at a wet coating thickness of 200 ⁇ m and dried at the atmosphere to remove the n-heptane.
  • the dried film was exposed for 20 s through a half-tone pattern in a DUPLIPHOT HS 130 (trade name of Agfa-Gevaert N.V. Belgium for a contact-­exposure apparatus) operating with eight 125 Watt mercury vapour lamps emitting UV-radiation.
  • the density (D) built up in the exposed area was 0.98.
EP86202055A 1985-11-26 1986-11-20 Verfahren zur Herstellung eines photothermographischen Materials Withdrawn EP0227141A1 (de)

Applications Claiming Priority (2)

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EP85201960 1985-11-26
EP85201960 1985-11-26

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5425993A (en) * 1991-06-24 1995-06-20 L'oreal Process for preparing submicron particles in the presence of lipid vesicles, and corresponding compositions
EP0775592A1 (de) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Wärmeempfindliches Bildaufzeichnungsverfahren
EP0775595A1 (de) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Wärmeempfindliches Auszeignungsmaterial, das Phosphorsäurederivaten als Schmiermitteln enthält
EP0779539A1 (de) 1995-11-27 1997-06-18 Agfa-Gevaert N.V. Thermographisches Material mit einer organischen antistatischen Aussenschicht
EP0782043A1 (de) 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Wärmeempfindliches Aufzeichnungsmaterial mit verbesserter Tonwiedergabe
EP0845709A1 (de) 1996-11-29 1998-06-03 Agfa-Gevaert N.V. Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung einer lithographischen Druckform damit
EP1371696A1 (de) * 2002-06-14 2003-12-17 Canon Kabushiki Kaisha Teilchenzusammensetzung und Verwendung der Teilchen in einem Aufzeichnungsverfahren und in einem Aufzeichnungsgerät
WO2004063240A1 (en) * 2003-01-10 2004-07-29 Canon Kabushiki Kaisha Micelle-containing composition, thin film thereof, and method for producing the thin film
WO2015148028A1 (en) 2014-03-24 2015-10-01 Carestream Health, Inc. Thermally developable imaging materials
WO2016073086A1 (en) 2014-11-04 2016-05-12 Carestream Health, Inc. Image forming materials, preparations, and compositions
WO2016195950A1 (en) 2015-06-02 2016-12-08 Carestream Health, Inc. Thermally developable imaging materials and methods
WO2017123444A1 (en) 2016-01-15 2017-07-20 Carestream Health, Inc. Method of preparing silver carboxylate soaps

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3457075A (en) * 1964-04-27 1969-07-22 Minnesota Mining & Mfg Sensitized sheet containing an organic silver salt,a reducing agent and a catalytic proportion of silver halide
FR2090961A5 (de) * 1970-04-29 1972-01-14 Agfa Gevaert Ag

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3457075A (en) * 1964-04-27 1969-07-22 Minnesota Mining & Mfg Sensitized sheet containing an organic silver salt,a reducing agent and a catalytic proportion of silver halide
FR2090961A5 (de) * 1970-04-29 1972-01-14 Agfa Gevaert Ag

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5670099A (en) * 1991-06-24 1997-09-23 L'oreal Process for preparing submicron particles in the presence of lipid vesicles, and corresponding compositions
US5425993A (en) * 1991-06-24 1995-06-20 L'oreal Process for preparing submicron particles in the presence of lipid vesicles, and corresponding compositions
EP0775592A1 (de) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Wärmeempfindliches Bildaufzeichnungsverfahren
EP0775595A1 (de) 1995-11-27 1997-05-28 Agfa-Gevaert N.V. Wärmeempfindliches Auszeignungsmaterial, das Phosphorsäurederivaten als Schmiermitteln enthält
EP0779539A1 (de) 1995-11-27 1997-06-18 Agfa-Gevaert N.V. Thermographisches Material mit einer organischen antistatischen Aussenschicht
EP0782043A1 (de) 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Wärmeempfindliches Aufzeichnungsmaterial mit verbesserter Tonwiedergabe
EP0845709A1 (de) 1996-11-29 1998-06-03 Agfa-Gevaert N.V. Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung einer lithographischen Druckform damit
US7300971B2 (en) 2002-06-14 2007-11-27 Canon Kabushiki Kaisha Particle composition, recording method, and recording apparatus using the particle composition
EP1371696A1 (de) * 2002-06-14 2003-12-17 Canon Kabushiki Kaisha Teilchenzusammensetzung und Verwendung der Teilchen in einem Aufzeichnungsverfahren und in einem Aufzeichnungsgerät
WO2004063240A1 (en) * 2003-01-10 2004-07-29 Canon Kabushiki Kaisha Micelle-containing composition, thin film thereof, and method for producing the thin film
WO2015148028A1 (en) 2014-03-24 2015-10-01 Carestream Health, Inc. Thermally developable imaging materials
US9335623B2 (en) 2014-03-24 2016-05-10 Carestream Health, Inc. Thermally developable imaging materials
WO2016073086A1 (en) 2014-11-04 2016-05-12 Carestream Health, Inc. Image forming materials, preparations, and compositions
US9523915B2 (en) 2014-11-04 2016-12-20 Carestream Health, Inc. Image forming materials, preparations, and compositions
WO2016195950A1 (en) 2015-06-02 2016-12-08 Carestream Health, Inc. Thermally developable imaging materials and methods
US9746770B2 (en) 2015-06-02 2017-08-29 Carestream Health, Inc. Thermally developable imaging materials and methods
WO2017123444A1 (en) 2016-01-15 2017-07-20 Carestream Health, Inc. Method of preparing silver carboxylate soaps

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