EP0609571A1 - Composés stilbèniques utilisés comme supersensibilisateurs dans des matériaux photographiques sensibles à l'IR - Google Patents

Composés stilbèniques utilisés comme supersensibilisateurs dans des matériaux photographiques sensibles à l'IR Download PDF

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Publication number
EP0609571A1
EP0609571A1 EP93200249A EP93200249A EP0609571A1 EP 0609571 A1 EP0609571 A1 EP 0609571A1 EP 93200249 A EP93200249 A EP 93200249A EP 93200249 A EP93200249 A EP 93200249A EP 0609571 A1 EP0609571 A1 EP 0609571A1
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Prior art keywords
alkyl
photographic material
hydrogen
material according
silver halide
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EP93200249A
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German (de)
English (en)
Inventor
Roland Claes
Jean-Marie Odil Dewanckele
Florin Seng
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP93200249A priority Critical patent/EP0609571A1/fr
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/164—Infrared processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/20—Methine and polymethine dyes with an odd number of CH groups with more than three CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/26—Polymethine chain forming part of a heterocyclic ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes

Definitions

  • the present invention relates to infrared sensitized photographic emulsions and materials, and more particularly to a specific class of supersensitizers for the infra-red spectral region.
  • Infra-red sensitized photographic materials are known for quite some time in photographic technology.
  • One of the well-known early applications was and still is in aerial photography.
  • the most familiar classes of infra-red sensitizing substances are long-chain cyanine dyes.
  • Suitable infra-red sensitizing dyes are disclosed in e.g. US-P Nos 2,095,854, 2,095,856, 2,955,939, 3,482,978, 3,552,974, 3,573,921, 3,582,344, 3,623,881 and 3,695,888.
  • the exposure source of the recording apparatus is a laser unit.
  • lasers as exposure units is situated in the field of radiographic monitoring photography where a hard copy of radiographic information has to be produced.
  • Other applications are situated in the pre-press field of phototype-setting and image-setting, where recorders are marketed which employ Ar ion lasers, He-Ne lasers or solid state semiconductor lasers, also called laserdiodes, as exposure source.
  • Ar ion lasers, He-Ne lasers or solid state semiconductor lasers, also called laserdiodes as exposure source.
  • the latter type of laser, the laserdiode shows some advantages compared to other laser types such as low cost price, small size, long life time and no need for an acoustic-optical modulator.
  • the emission wavelength of these semiconductor laser beams is longer than 700 nm and mostly longer than 750 nm.
  • photographic materials appropriate for exposure by devices employing such laserdiodes must be sensitized for the near infra-red region of the radiation spectrum.
  • Suitable photographic materials to be used with semiconductor laser device are disclosed in Japanese Unexamined Patent Publication (Kokai) No 61752/85 and US-P 4,784,933.
  • Commercial infra-red sensitized film and paper were announced by Eastman Kodak Co in "Proceedings Lasers in Graphics, Electronic Publishing in the '80's, Vol 2 (sept. 1985) p. 508, and put on the market lateron.
  • Other manufacturers followed including Agfa-Gevaert N.V. and Fuji Photo Film Co.
  • An example of an image-setter using a laserdiode exposure is the PROSET 9800 apparatus marketed by Miles Inc., Agfa division.
  • a permanent problem in the field of imaging by laserdiodes is the sensitivity level of the infra-red sensitized photographic material.
  • a first reason for that is made up by the low energy output of the laserdiode which is in the order of a few milli-Watts.
  • a second problem consists in the usually poor storage quality of emulsions sensitized with long-chain cyanine dyes unless considerable amounts of stabilizers are used ; however it is generally known that such a strong stabilization tends to reduce the original sensitivity level.
  • Supersensitization can be achieved by a combination of at least two spectral sensitizers giving rise to a level of sensitization in some spectral region which is greater than that which would result from any concentration of either dye alone or from the mere additive effect of the dyes.
  • supersensitization can be achieved with selected combinations of spectral sensitizing dyes and other addenda such as stabilizers, anti-foggants, development accelerators or inhibitors, coating aids, brighteners and antistatic agents.
  • a general review on supersensitization is given in James, The Theory of the Photographic Process, Fourth Edition, 1977, pp. 259-265. Several possible mechanisms concerning supersensitization are discussed by Gilman, Photographic Science and Engineering, Vol. 18, 1974, pp. 418-430.
  • a class of effective supersensitizers comprises water-soluble heterocyclic mercapto-compounds containing a thiazole, benzothiazole, naphthothiazole, or quinoline ring system, which ring system may be substituted or not, and also comprising at least one electronegative group e.g. halogen, sulfo, sulphonamide, carboxy and phenyl.
  • These compounds are preferably combined with penta- or heptamethine cyanine dyes, or tetramethine merocyanine dyes sensitizing in the near infra-red spectral region.
  • Stilbene derivatives are known for a long time in the art as effective supersensitizers in combination with infra-red sensitizing dyes.
  • US 3,695,888, issued 3 Oct. 1972 discloses sulphonated bis(1,3,5-triazine-2-ylamino)-stilbene compounds in combination with some particular type of tricarbocyanine dyes.
  • US 4,603,104 claims the combination of infra-red sensitized emulsions, bis(1,3,5-triazine-2-ylamino)-stilbene compounds and some particular stabilizers, e.g. arylmercaptotetrazoles.
  • US 4,677,053 discloses infra-red sensitizers containing a quinoline nucleus in combination with bis(1,3,5-triazine-2-ylamino)-stilbenes.
  • Unexamined Japanese Patent Publication 61-134755 describes the combination of benzopyrylocyanine dye and a bis-triazinyl- or bis-pyrimidyl-iminostilbene.
  • Unexamined Japanese Patent Publications 62-035343 and 01-097947 disclose some hexamethine rhodanine type sensitizers in combination with stilbene derivatives.
  • the present invention extends the teachings on stilbene compounds as useful supersensitizers for the near infra-red region.
  • a photographic material comprising a support and at least one emulsion layer containing a silver halide emulsion, an infrared sensitizer and a stilbene compound corresponding to general formula (SS-Ia): wherein M represents a hydrogen ion or a monovalent cation, R1 and R2 each independently represent hydrogen, alkyl, alkoxy, NR3R4, SO2R3, COOR3, CONR3R4, NR3COR4, or SO3M, and Z1 and Z2 each independently represent Cl, OH, NR3R4, OR5 or SR5, and, R3, R4 and R5 each independently represent alkyl, aryl or hydrogen.
  • M represents a hydrogen ion or a monovalent cation
  • R1 and R2 each independently represent hydrogen, alkyl, alkoxy, NR3R4, SO2R3, COOR3, CONR3R4, NR3COR4, or SO3M
  • Z1 and Z2 each independently represent Cl, OH, NR3R4,
  • the most effective supersensitizers are those where Z1 and Z2 represent naphthoxy groups too, thus making a total of four unsubstituted or substituted naphthoxy groups on the triazine nuclei.
  • a preferred class of stilbene derivatives is formed by those whose two triazine nuclei each bear two unsubstituted or substituted naphthoxy groups (four naphthoxy groups in total), given by general formula (SS-Ib): wherein the different R groups have the same meaning as in general formula (SS-Ia).
  • a most preferred supersensitizer according to general formula (SS-Ib) is represented by:
  • Other preferred stilbene supersensitizers for use in accordance with the present invention bearing only one naphthoxy group on each triazine nucleus are represented by following formulae SS-I2 and SS-I3 : It will be easily recognized that the stilbene derivatives can exhibit cis-trans isomerism around the central double bond. It was experimentally found by us that for compounds SS-I1 and SS-I2 the actual isomeric form (cis, trans or a mixture of both) did not influence their photographic behavior.
  • Stilbene compounds not belonging to the scope of the invention but useful as control compounds in photographic examples are listed below :
  • a conventional non-stilbene control supersensitizer is compound SHM1 from Research Disclosure 28952, cited above. This compound is designated as SS-C10 furtheron in the photographic examples:
  • Preferred infra-red sensitizing dyes used in accordance with the present invention are heptamethine chain containing infra-red sensitizers represented by general formula : wherein,
  • IR-sensitizers represented by this general formula are the following compounds :
  • the infra-red sensitizing dyes and the supersensitizers in connection with the present invention are all incorporated in the emulsion layer(s) of the photographic material in order to exercise their photographic functions properly.
  • the IR-sensitizers are usually added as solutions in an organic solvent.
  • the supersensitizers are preferably added as methanolic solutions in a concentration ranging from about 0.1 % to about 1 %.
  • the solubility in methanol depends on the cationic form. For instance, the lithium salt analogue of compound (SS-I1) is better soluble (about 1 %) than the sodium salt (about 0.3 %).
  • the supersensitizers used in accordance with the present invention remain dissolved without problems, which, for instance, is not the case with the compound, analogue to preferred compound (SS-I1) but bearing phenoxy substituents instead of naphthoxy ones.
  • the stilbene supersensitizers are preferably added to the silver halide emulsion in a concentration ranging from 0.01 mmole to 10 mmole per mole of silver halide.
  • the infra-red sensitizing dyes are present in the emulsion preferably in a concentration between 0.01 mole and 1 mmole per mole of silver halide.
  • the supersensitizers are added preferably before the infra-red sensitizing dyes, but they can be added also after the sensitizers or simultaneously. In normal practice only one effective supersensitizer is added but in principle a mixture of more than one can be used.
  • the emulsion layer of the photographic material consists of a single layer but principally a double or even a multiple emulsion layer can be present.
  • the halide composition of the silver halide emulsions used according to the present invention is not specifically limited and may be any composition selected from e.g. silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide.
  • the photographic emulsions can be prepared from soluble silver salts and soluble halides according to different methods as described e.g. by P. Glafkidès in “Chimie et Physique Photographique”, Paul Montel, Paris (1967), by G.F. Duffin in “Photographic Emulsion Chemistry", The Focal Press, London (1966), and by V.L. Zelikman et al in “Making and Coating Photographic Emulsion", The Focal Press, London (1966). They can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition.
  • the silver halide can be precipitated according to the single-jet method, the double-jet method, the conversion method or an alternation of these different methods.
  • the silver halide particles of the photographic emulsions used according to the present invention may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
  • the silver halide grains may have a multilayered grain structure. According to a simple embodiment the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of dopes. Besides having a differently composed core and shell the silver halide grains may also comprise different phases inbetween.
  • Two or more types of silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in accordance with the present invention.
  • the average size of the silver halide grains may range from 0.05 to 1.0 micron, preferably from 0.2 to 0.5 micron.
  • the size distribution of the silver halide particles can be homodisperse or heterodisperse.
  • the silver halide crystals can be doped with Rh3+, Ir4+, Cd2+, Zn2+ or Pb2+.
  • the emulsion can be desalted in the usual ways e.g. by dialysis, by flocculation and re-dispersing, or by ultrafiltration.
  • the light-sensitive silver halide emulsions are preferably chemically sensitized as described e.g. in the above-mentioned "Chimie et Physique Photographique” by P. Glafkidès, in the above-mentioned “Photographic Emulsion Chemistry” by G.F. Duffin, in the above-mentioned “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen Sawe mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines.
  • the emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au.
  • One of these chemical sensitization methods or a combination thereof can be used.
  • the silver halide emulsion(s) for use in accordance with the present invention may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements or during the photographic treatment thereof.
  • Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion. Suitable examples are e.g.
  • heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, oxazoline-thione, triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z.
  • benzothiazolium salts such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercapto
  • Particularly useful stabilizer compounds in the practice of this invention are substituted mercaptotetrazoles, examples of which are listed below: It was found by us that the nature and concentration of the mercaptotetrazole used played a crucial role in obtaining the maximally reachable sensitivity even when the optimal combination of infra-red sensitizer and supersensitizer was chosen. This will be illustrated with an example furtheron.
  • the fog-inhibiting agents or stabilizers can be added to the silver halide emulsion prior to, during, or after the ripening thereof and mixtures of two or more of these compounds can be used.
  • the binder is a hydrophilic colloid, preferably gelatin.
  • Gelatin can, however, be replaced in part or integrallly by synthetic, semi-synthetic, or natural polymers.
  • Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • the semi-synthetic substitutes for gelatin are modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
  • modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin
  • cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
  • the binders of the photographic element can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and
  • the photographic material can contain several non light sensitive layers, e.g. a protective top layer, one or more backing layers, and one or more intermediate layers which can contain light-absorbing dyes.
  • Suitable light-absorbing dyes are described in e.g. US 4,092,168, US 4,311,787 and DE 2,453,217.
  • Such light-absorbing dyes can exercise several photographic functions. They can be used as filter dyes. They can also function as so-called screening dyes in order to promote image sharpness. Very important is the use of light-absorbing dyes as antihalation dyes in order to reduce the reflection of light by a transparent support onto the light sensitive layer(s).
  • a preferred infrared absorbing dye is represented by following formula (FD-1) :
  • the infra-red sensitized photographic materials of the present invention are preferably manufactured and treated in severe safelight conditions, e.g. faint cyan light, or in total darkness.
  • One or more backing layers can be provided at the non-light sensitive side of the support. These layers which can serve as anti-curl layer can contain e.g. lubricants, antistatic agents, light absorbing dyes, matting agents, silica, etc.
  • the photographic element of the present invention may further comprise various kinds of surface-active agents in the photographic emulsion layer or in at least one other hydrophilic colloid layer.
  • Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides e.g.
  • polyethylene glycol polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring
  • Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
  • Preferred surface-active coating agents are compounds containing perfluorinated alkyl groups.
  • the photographic elements in connection with the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents and plasticizers.
  • Suitable additives for improving the dimensional stability of the photographic elements are e.g. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl(meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins, and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, Alpha-Beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
  • a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl(meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters,
  • Spacing agents can be present, preferably in the top protective layer; in general the average particle size of such spacing agents is comprised between 0.2 and 10 micron. They can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath. Suitable spacing agents can be made e.g. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US 4,614,708.
  • the support of the photographic materials in connection with the present invention can be transparent base, preferably an organic resin support, e.g. cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, polyvinylchloride film or poly-Alpha-olefin films such as polyethylene or polypropylene film.
  • the thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm.
  • These organic resin supports are preferably coated with a subbing layer.
  • the support of the photographic material can be a paper base preferably a polyethylene or polypropylene coated paper base.
  • the photographic materials according to the invention can be processed by any means or any chemicals known in the art depending on their particular application.
  • infra-red sensitive elements in the field of graphic arts for phototype- or image-setting they are preferably processed in so-called "Rapid Access” chemicals, comprising a conventional Phenidone/hydrochinon developing solution and a conventional sodium or ammonium thiosulphate containing fixing solution.
  • the development time is usually between 10 and 30 seconds at a temperature of about 35 °C.
  • they can be processed in so-called "hard dot Rapid Access” chemistry, e.g. the AGFASTAR system marketed by Agfa-Gevaert N.V..
  • an automatically operated processor provided with automatic regeneration is used, e.g. a RAPILINE device marketed by Agfa-Gevaert N.V..
  • a small amount of hydroquinone was added as an anti-oxidant.
  • THe pH was adjusted to 5.0.
  • the emulsion was coated at an amount of silver halide corresponding to 4.27 g Ag/m2 and at 2.5 g/m2 of gelatin.
  • the photosensitive layer was overcoated with a layer containing 1 g/m2 of gelatin, a matting agent and formaldehyde as gelatin hardener. Surfactants were added to both layers as coating aids.
  • the coated samples were exposed on a laser-sensitometer using a 780 nm laserdiode and a continuous wedge with a wedge constant of 0.10 log H/cm.
  • the sensitivity expressed as relative log H value, was measured at a density of 3.00 above fog. A higher number means more sensitive. So an increase by a value of 0.30 means a doubling of speed.
  • the sensitivity of sample 1.2. was arbitrarily set at 1.00.
  • IRS-1 1.1 IRS-1 (0.039) no supersensitizer - 1.2 " (0.039) SS-C10 (0.529) 1.00 1.3 " (0.039) SS-C1 (0.103) 0.50 1.4 IRS-2 (0.039) SS-C1 (0.103) 0.60 1.5 IRS-1 (0.051) SS-C2 (0.211) 0.30 1.6 " (0.051) SS-C3 (0.211) 0.40 1.7 " (0.051) SS-C4 (0.157) 0.20 1.8 " (0.051) SS-C5 (0.157) 0.20 1.9 " (0.051) SS-C6 (0.157) 0.30 1.10 " (0.051) SS-C7 (0.157) 0.20 1.11 " (0.051) SS-C8 (0.157) 0.20 1.12 “ (0.051) SS-C9 (0.157) 0.60 1.13 " (0.039) SS-I1 (0.103) 1.20 1.14 IRS-2 (0.039) SS-I1 (0.103) 0.90 1.15 IRS-1 (0.051)
  • a sulfur plus gold sensitized cubic silver halide emulsion was prepared consisting of 2 % iodide and 98 % bromide, and showing an average grain size of 0.24 micron.
  • a conventional substituted tetraazaindene as antifoggant agent.
  • sensitizer IRS-1 and supersensitizer SS-I1 as shown in table 2.
  • a small amount of hydroquinone was added as an anti-oxidant. The pH was adjusted to 6.00.
  • the emulsion was coated on a transparent support at a coverage of an amount of silver halide corresponding to 3.56 g Ag/m2 and at 2.2 g/m2 of gelatin.
  • the photosensitive layer was overcoated with a layer containing 1 g/m2 of gelatin, a matting agent and formaldehyde as gelatin hardener. Surfactants were added to both layers as coating aids.
  • the samples were processed in an automatic processor using a so-called "hard dot Rapid Access” developer, a conventional fixer containing ammonium thiosulphate, and water as rinsing liquid.
  • the development time was 40 s at 38 C.
  • the results of table 2 indicate a strong supersensitization effect of the supersensitizer SS-I1 according to the invention, compared with a conventional supersensitizer. Furtheron the results of table 2 compared with the results of table 1 (samples 2.3 and 1.13) show that on an emulsion with a high bromide concentration the supersensitization effect is even stronger than on an emulsion rich in chloride. A conventional supersensitizer shows this effect to a much less extent (compare samples 1.2 and 2.2).
  • a photographic element was coated on a opaque resin coated paper.
  • the element consisted of three layers : an "undercoat", a photosensitive layer and a protective layer.
  • the "undercoat” contained 1.1 g/m2 of TiO2 (BAYERTITAN AN2, marketed by Bayer AG) and 1.0 g/m2 of gelatin.
  • the photosensitive layer contained the same emulsion and ingredients as in example 1. Supersensitizers and dyes were added as indicated in table 3. Furtheron, an infrared absorbing filter dye (FD-1) was added at 67 mg/m2.
  • the emulsion was coated at an amount of silver halide corresponding to 1.43 g Ag/m2 and at 1.32 g/m2 of gelatin.
  • the photosensitive layer was overcoated with a layer containing 1 g/m2 of gelatin, a matting agent and formaldehyde as gelatin hardener. Surfactants were added to all three layers as coating aids.
  • chlorobromoiodide emulsion was prepared as example 1. To 1 kg emulsion, containing 1.10 moles of silver halide, was added a conventional substituted tetraazaindene as antifoggant agent each in an experimentally optimized concentration. Then various mercaptotetrazoles were added to aliquot portions of the emulsion as shown in table 4. A small amount of hydroquinone was added as an anti-oxidant. Supersensitizer SS-I1 and dye IRS-1 were added in an amount of 0.211 and 0.051 mmoles per mole of silver halide respectively.
  • the emulsion was coated at an amount of silver halide corresponding to 4.27 g Ag/m2 and at 2.5 g/m2 of gelatin.
  • the photosensitive layer was overcoated with a layer containing 1 g/m2 of gelatin, a matting agent and formaldehyde as gelatin hardener. Surfactants were added to both layers as coating aids.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP93200249A 1993-02-01 1993-02-01 Composés stilbèniques utilisés comme supersensibilisateurs dans des matériaux photographiques sensibles à l'IR Withdrawn EP0609571A1 (fr)

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EP93200249A EP0609571A1 (fr) 1993-02-01 1993-02-01 Composés stilbèniques utilisés comme supersensibilisateurs dans des matériaux photographiques sensibles à l'IR

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0821272A1 (fr) * 1996-07-24 1998-01-28 Agfa-Gevaert N.V. Produit d'enregistrement, photothermographique comprenant des colorants sensibilisateurs de l'infra-rouge
EP0821271A1 (fr) * 1996-07-24 1998-01-28 Agfa-Gevaert N.V. Produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene
US5958667A (en) * 1996-07-24 1999-09-28 Agfa-Gevaert Photothermographic recording material comprising IR-sensitizing dyes
KR102040849B1 (ko) * 2018-08-17 2019-11-05 건국대학교 산학협력단 쿠마린을 포함하는 신규한 스틸벤 유도체, 이의 제조 방법 및 이를 포함하는 형광증백제 조성물

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0126455A2 (fr) * 1983-05-19 1984-11-28 Fuji Photo Film Co., Ltd. Emulsion photographique à halogénure d'argent
US4677053A (en) * 1983-04-15 1987-06-30 Yuji Mihara Silver halide photographic materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4677053A (en) * 1983-04-15 1987-06-30 Yuji Mihara Silver halide photographic materials
EP0126455A2 (fr) * 1983-05-19 1984-11-28 Fuji Photo Film Co., Ltd. Emulsion photographique à halogénure d'argent

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0821272A1 (fr) * 1996-07-24 1998-01-28 Agfa-Gevaert N.V. Produit d'enregistrement, photothermographique comprenant des colorants sensibilisateurs de l'infra-rouge
EP0821271A1 (fr) * 1996-07-24 1998-01-28 Agfa-Gevaert N.V. Produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene
US5958667A (en) * 1996-07-24 1999-09-28 Agfa-Gevaert Photothermographic recording material comprising IR-sensitizing dyes
KR102040849B1 (ko) * 2018-08-17 2019-11-05 건국대학교 산학협력단 쿠마린을 포함하는 신규한 스틸벤 유도체, 이의 제조 방법 및 이를 포함하는 형광증백제 조성물

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