EP0666496A1 - Photographische, Infrarot-sensibilisierende farbstoffenthaltende Silberhalogenidelemente - Google Patents

Photographische, Infrarot-sensibilisierende farbstoffenthaltende Silberhalogenidelemente Download PDF

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Publication number
EP0666496A1
EP0666496A1 EP94101874A EP94101874A EP0666496A1 EP 0666496 A1 EP0666496 A1 EP 0666496A1 EP 94101874 A EP94101874 A EP 94101874A EP 94101874 A EP94101874 A EP 94101874A EP 0666496 A1 EP0666496 A1 EP 0666496A1
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EP
European Patent Office
Prior art keywords
infrared sensitizing
silver halide
infrared
dye
sensitizing dyes
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EP94101874A
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English (en)
French (fr)
Inventor
Ivano Delprato
Stefania Ghirardo
Antonio Luzzi
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Eastman Kodak Co
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Minnesota Mining and Manufacturing Co
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Priority to EP94101874A priority Critical patent/EP0666496A1/de
Priority to JP1904395A priority patent/JPH07230139A/ja
Publication of EP0666496A1 publication Critical patent/EP0666496A1/de
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—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
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/164—Infrared processes

Definitions

  • the present invention relates to a process for stabilizing a solution of infrared sensitizing dyes and to silver halide photographic elements comprising a layer containing such infrared sensitizing dyes.
  • silver halide photographic elements can be spectrally sensitized to infrared radiation. See Mees and James, The Theory of Photographic Processes , 3rd edition, The McMillan Company, 1966, pages 198 and 199. Silver halides are intrinsically sensitive only to light in the blue region of the spectrum. Therefore, when silver halides are to be exposed to other wavelengths of radiation, such as green light, red light or infrared radiation, a spectral sensitizing dye is required to render silver halide sensitive to such radiation. As known in the art, silver halides having adsorbed on the grains spectral sensitizing dyes can be made sensitive to radiation of a wavelength other than the intrinsic blue sensitivity.
  • Tricarbocyanine is a term used in the art to include dyes having an amidinium-ion cromophoric system (see Mees and James above, page 201). Tricarbocyanine infrared sensitizing dyes are also described in US Patent Nos. 4,536,473, 4,959,294, 5,061,618, 4,619,892, 3,506,655, 3,552,974, 3,623,881 and 3,758,461.
  • the infrared sensitizing dyes can be directly dispersed in the emulsion, or, alternatively, they may be first dissolved in a suitable solvent to add them to the emulsion as a solution.
  • Processes for adding the infrared sensitizing dye to the photographic emulsion are described in US Pat. Nos. 3,469,987, 3,676,147, 3,822,135, 4,199,360, 2,912,343, 3,342,605, 2996,287 and 3,429,835.
  • infrared sensitizing dye A problem with many known infrared sensitizing dye is the poor stability of their solutions during keeping which renders them of limited utility in making photographic elements. In fact, the solution of infrared sensitizing dyes must be added to silver halide emulsion within few hours after being made, otherwise the solution rapidly degrades and loses the sensitizing effect.
  • US Patent No. 5,147,756 describes a process for stabilizing an aqueous solution of aryl hydrazides. These solutions may be made by the addition of a stabilizing amount of ascorbic acid, tartaric acid, citric acid, glucose and the like. The aqueous solutions have longer shelf-life.
  • the stabilized aryl hydrazide is useful in photographic silver halide emulsion to produce very high contrast images in graphic arts materials.
  • US Patent No. 5,037,734 describes a photographic silver halide emulsion spectrally sensitized in the infrared region of the electromagnetic spectrum, said emulsion being stabilized by the combination of an organic reducing agent having an oxidation potential from about +0.10 to about +0.70 volts vs SCE (Saturated Calomel Electrode), such as ascorbic acid or dihydroanhydropiperidino hexose reductone, and a nonionic surface active agent capable of deaggregating the infrared sensitizing dye.
  • an organic reducing agent having an oxidation potential from about +0.10 to about +0.70 volts vs SCE (Saturated Calomel Electrode), such as ascorbic acid or dihydroanhydropiperidino hexose reductone
  • a nonionic surface active agent capable of deaggregating the infrared sensitizing dye.
  • This patent solves the problem of stabilizing an emulsion spectrally sensitized in the infrared region, while a process for stabilizing a solution containing an infrared sensitizing dye to be added to the emulsion some hours later, during the coating phase, is not therein mentioned.
  • Ascorbic acid is also known in the art as supersentizer in light-sensitive materials having high sensitivity and excellent color reproduction.
  • US Patent No. 4,917,997 describes a silver halide photographic emulsion combined with an ascorbic acid compound, a bisaminostilbene compound substituted by a pyrimidine derivative and one sensitizing dye, said photographic emulsion exhibiting an increased spectral sensitivity.
  • US Patent No. 4,897,343 describes a spectrally sensitized silver halide photographic emulsion comprising at least one alkali metal sulfite compound and at least one ascorbic acid compound as supersensitizing agents for a spectrally sensitized dye.
  • Ascorbic acid is also known in the art as reduction sensitizing agent during the emulsion making process.
  • European Patent Application No. 371,338 describes a monodisperse silver halide emulsion reduction-sensitized during precipitation of silver halide grains in the presence of a thiosulphonic acid compound or by ascorbic acid in a process of manufacturing a silver halide emulsion.
  • Process of manufacturing silver halide emulsions are roughly classified into, e.g., grain formation, desalting, chemical sensitization and coating steps. Grain formation is further classified into, e.g., nucleation, ripening and precipitation substeps.
  • European Patent Application No. 404,142 describes a process for treating a tabular silver halide emulsion comprising the steps of subjecting the emulsion to reduction sensitization by ascorbic acid and subjecting the tabular emulsion in the presence of a nitrogen-containing hetrocyclic compound which forms a complex with silver to sulfur sensitization, selenium sensitization or gold sensitization during the manufacture of the tabular emulsion.
  • the present invention refers to a process for stabilizing solutions of infrared sensitizing dyes.
  • it refers to a process wherein a stabilizing amount of an organic reducing agent and of an organic or inorganic buffering agent has been used to increase the stability of the solution of infrared sensitizing dyes.
  • the present invention relates to a silver halide photographic element comprising a support, at least one infrared sensitive silver halide emulsion photosensitive layer and at least one hydrophilic colloid non photosensitive layer, wherein at least one infrared sensitive layer contains an infrared sensitizing dye and a stabilizing amount of an organic reducing agent and of an organic or inorganic buffering agent.
  • the process of the present invention allows to obtain solutions of infrared sensitizing dyes which maintain their stability during keeping, without loosing the sensitizing effect. This fact allows to add said solutions of infrared sensitizing dyes to the photographic material up to at least 2 days after the preparation, rather than very few hours as done in the past. An improvement in the photographic speed is also obtained by using stabilized solutions of infrared sensitizing dyes in silver halide photographic elements.
  • the infrared sensitizing dyes to be used in the present invention may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixture thereof to add them to the silver halide emulsion as a solution.
  • a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixture thereof.
  • the solution contains generally 0.02% to 1.0% by weight of the infrared sensitizing dye and must be added to the silver halide emulsion within 1-12 hours after being made. Otherwise, the solution degrades rapidly and its sensitizing effect decreases.
  • a stabilizing amount of an organic reducing agent and of an organic or inorganic alkaline buffering agent is used to stabilize said solutions of infrared sensitizing dyes.
  • the solvent used to dissolve the infrared sensitizing dyes used in this invention is a mixture of water and alcohol (such as methyl alcohol, ethyl alcohol, phenyl cellosolve, and the like) or water alone.
  • Said organic reducing agent is selected from the group consisting of ascorbic acid, an ascorbic acid isomer, glucose, cyclodextrin and a mixture thereof, while said organic and inorganic buffering agent is selected from the group consisting of alkali metal (e.g., sodium, potassium, lithium, and the like) acetate, citrate, phosphate, borate, tartarate and the like.
  • alkali metal e.g., sodium, potassium, lithium, and the like
  • the organic reducing agent is ascorbic acid or an ascorbic acid derivative (e.g., ascorbic acid, L-ascorbic acid, sodium L-ascorbate, sodium D-ascorbate, and the like).
  • the amount of said organic reducing agent is in the range of from 5 to 500 mg, preferably in the range of from 10 to 300 mg, most preferably in the range of from 20 to 200 mg for 100 ml of solution containing 0.1% by weight of sensitizing dye.
  • the alkaline buffering agent is sodium acetate.
  • the amount of said alkaline buffering agent is in the range of from 20 to 1000 mg, preferably in the range of from 100 to 500 mg per 100 ml of solution containing 0.1% by weight of sensitizing dye.
  • the preferred process of the present invention comprises dissolving the infrared sensitizing dye in phenylcellosolve solvent and heating at 50°C to obtain a solution and, then, adding methyl alcohol and a desired amount of sodium acetate and ascorbic acid.
  • the resulting solution is made up to 100 ml with methanol at 20°C.
  • the solutions obtained with the reducing agent and the buffering agent are clear and retain their stability for a reasonable length of time e.g. at least 2 days versus only few hours without the reducing and buffering agents.
  • the solutions with the reducing and buffering agents used in the present invention show no solids, while the solutions without reducing and buffering agents form solids after a short period of time, e.g., 1 to 12 hours.
  • Said stabilized solutions of infrared sensitizing dyes may be kept in storage conditions to be added later to the silver halide emulsion just before coating on a suitable support, without loosing the sensitizing effect even if they are not added to the silver halide emulsion immediately after their preparation.
  • Infrared sensitizing dyes which can be used in the present invention include those which are represented by the following general formula (I): wherein, Z1 and Z2 each independently represents the atoms necessary to complete a substituted or unsubstituted 5- or 6-membered heterocyclic nucleus R1 and R2 each independently represents a substituted or unsubstituted alkyl group, L1, L2, L3, L4 and L5 each independently represents a substituted or unsubstituted methine group, X- represents an anion, n represents an integer of 1 to 2, provided that n is 1 when the dye forms an intramolecular salt, p and q each independently represents 0 or 1, and z represents 2.
  • Z1 and Z2 each independently represents the atoms necessary to complete a substituted or unsubstituted 5- or 6-membered heterocyclic nucleus
  • R1 and R2 each independently represents a substituted or unsubstituted alkyl group
  • Z1 and Z2 each independently represents the atoms necessary to complete a substituted or unsubstituted 5- or 6-membered heterocyclic nucleus.
  • These include a substituted or unsubstituted thiazole nucleus, quinoline nucleus, tellurazole nucleus, pyridine nucleus, thiazoline nucleus, oxazole nucleus, selenazole nucleus, and the like.
  • These nuclei may be substituted by any of a number of groups known to be substituents for such nuclei. These includes sulfo, halogen (e.g.
  • alkyl of 1 to 12 carbon atoms preferably of about 1 to 4 carbon atoms, e.g. methyl, ethyl, butyl, which may themselves be substituted with known elements such as hydroxy, halogen or sulfo
  • alkoxy of 1 to 12 carbon atoms preferably of about 1 to 4 carbon atoms, e.g., methoxy, ethoxy, butoxy
  • carboxy carboxylate of from 1 to 4 carbon atom (e.g., methyl ester, ethyl ester), sulfonamido or carbonamido.
  • R1 and R2 each independently represents a substituted or unsubstituted alkyl of 1 to 20 carbon atoms (preferably of from 1 to 6 carbon atoms).
  • alkyl include methyl, ethyl, propyl, isopropyl, butyl, octyl, etc.
  • substituted alkyl groups preferably a substituted lower alkyl of from 1 to 6 carbon atoms
  • a hydroxyalkyl group e.g., ⁇ -hydroxyethyl, ⁇ -hydroxypropyl, ⁇ -hydroxybutyl, etc.
  • a carboxyalkyl group e.g., ⁇ -carboxyethyl, ⁇ -carboxypropyl, etc.
  • a sulfoalkyl group e.g., ⁇ -sulfoethyl, ⁇ -sulfopropyl, ⁇ -sulfobutyl, ⁇ -sulfobutyl, etc.
  • a sulfatoalkyl group e.g., ⁇ -sulfatoethyl, ⁇ -sulfatopropyl, etc.
  • an acyloxyalkyl group e.g., ⁇ -acetoxyethyl, ⁇ -acetoxy
  • substituents on the methine groups may form bridged linkages.
  • L2, L3 and L4 methine groups may be bridged to form a 6-membered substituted or unsubstituted carbocyclic ring.
  • L3, L4 and L5 methine groups may be bridged to form a 5- or 6-membered substituted or unsubstituted carbocyclic ring.
  • Preferred infrared sensitizing dyes which can be used in the present invention include those which are represented by the following general formula (II): wherein, Z3 and Z4 each independently represents the atoms necessary to complete a substituted or unsubstituted thiazole nucleus or a substituted or unsubstituted oxazole nucleus, or a substituted or unsubstituted selenazole nucleus, Q represents the atoms necessary to complete a substituted or unsubstituted 5- or 6-membered carbocyclic ring, R1 and R2 each independently represents a substituted or unsubstituted alkyl group, R3 represents hydrogen, alkyl of 1 to 4 carbon atoms, aryl, cyano, halogen or - NR4R5, wherein R4 and R5 each independently represents alkyl of 1 to 6 carbon atoms or aryl or together represent the non-metallic atoms necessary to form a substituted or unsubstitute
  • Z3 and Z4 each independently represents the atoms necessary to complete a substituted or unsubstituted thiazole nucleus or oxazole nucleus or a substituted or unsubstituted selenazole nucleus.
  • These nuclei may be substituted by any of a number of groups known to be substituents for such nuclei. These includes sulfo, halogen (e.g. chloro, fluoro), alkyl of 1 to 12 carbon atoms (preferably of about 1 to 4 carbon atoms, e.g.
  • methyl, ethyl, butyl which may themselves be substituted with known elements such as hydroxy, halogen or sulfo), alkoxy of 1 to 12 carbon atoms (preferably of about 1 to 4 carbon atoms, e.g. methoxy, ethoxy, butoxy), carboxy, carboxylate of from 1 to 4 carbon atom (e.g. methyl ester, ethyl ester), sulfonamido or carbonamido.
  • useful nuclei for Z3 and Z4 include a thiazole nucleus, e.g.
  • thiazole 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)-thiazole, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methybenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-phenylbenzothiazole, 6-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, te
  • benzoxazole 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methyl-benzoxazole, 5,6-dimethyl-benzoxazole, 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc., a naphthoxazole nucleus, e.g. ⁇ -naphthoxazole, ⁇ -naphthoxazole, etc., or a selenazole nucleus, e.g.
  • benzoselenazole 5-chlorobenzoselenazole, 5-methylbenzoselenazole, 5-phenylbenzoselenazole, 6-methylbenzoselenazole, 5,6-dimethyl-benzoselenazole, 4,6-dimethylbenzoselenazole, 5-methoxybenzoselenazole, 5-ethoxybenzoselenazole, 5-chlorobenzoselenazole, 6-methoxybenzo-selenazole, 5-hydroxybenzoselenazole, 6-hydroxybenzoselenazole, etc., a naphthoselenazole nucleus, e.g. ⁇ -naphthoselenazole, ⁇ -naphthoselenazole, etc.
  • R1 and R2 each represent a substituted or unsubstituted alkyl as defined for formula (I) above.
  • R3 represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms (such as methyl, ethyl, propyl), an aryl group (such as phenyl), cyano, halogen (such as chloro, bromo, fluoro) or -NR4R5, wherein R4 and R5 each independently represents an alkyl group of 1 to 6 carbon atoms (such as methyl, ethyl, propyl), an aryl group (such as phenyl, p-methoxyphenyl) or together represent the non-metallic atoms necessary to form a substituted or unsubstituted 5- or 6-membered heterocyclic ring group.
  • R4 and R5 each independently represents an alkyl group of 1 to 6 carbon atoms (such as methyl, ethyl, propyl), an aryl group (such as phenyl, p-methoxyphenyl) or together represent the non-metallic atoms necessary to
  • said heterocyclic ring group is a heterocyclic aromatic ring including two conjugated double bonds in the ring.
  • the aromatic character of said heterocyclic rings is well known in the chemical literature, as described for example in S.H. Pine, Organic Chemistry , Fifth Edition, MacGraw-Hill Book Company, 1987, page 703.
  • This ring may be substituted as known in the art.
  • substituents include alkyl such as alkyl from 1 to 4 carbon atoms (e.g. methyl, ethyl, butyl), which may themselves be substituted with known elements such as hydroxy, halogen and the like (e.g., hydroxyethyl, chloroethyl), carboxylate of from 1 to 4 carbon atom (e.g.
  • 5-membered N-containing aromatic ring examples include pyrazole, triazole, imidazole and pyrrole.
  • Q represents the atoms necessary to complete a substituted or unsubstituted 5- or 6- membered carbocyclic ring.
  • This ring can be substituted, as known to one skilled in the art.
  • substituents include substituted or unsubstituted alkyl of 1 to 12 carbon atoms (e.g., methyl, ethyl, propyl, chloroethyl, benzyl), substituted or unsubstituted aryl (e.g., phenyl, p-chlorophenyl), halogen (e.g., chloro, fluoro), hydroxy, alkoxy (e.g., methoxy, ethoxy) and other conventional dyes substituents that would be apparent to one skilled in the art.
  • the anion represented by X ⁇ is for example, a halogen ion (e.g., chloride, bromide, iodide), p-toluene sulfonate (PTS ⁇ ), ethylsulfonate, perchlorate, or the like.
  • a halogen ion e.g., chloride, bromide, iodide
  • PTS ⁇ p-toluene sulfonate
  • ethylsulfonate ethylsulfonate
  • perchlorate or the like.
  • alkyl group includes not only such alkyl moieties as methyl, ethyl, octyl, stearyl, etc., but also such moieties bearing substituents groups such as halogen, cyano, hydroxyl, nitro, amine, carboxylate, etc.
  • alkyl moiety includes only methyl, ethyl, octyl, stearyl, cyclohexyl, etc.
  • infrared absorbing dyes examples include the following; however the scope of this invention is not limited to them.
  • the infrared senziting dyes for use in the present invention can be prepared according to well-known procedures in the art, such those described in James, The Theory of Photographic Processes , MacMillan, 4th Edition, 1977, in US Pat. Nos. 2,734,900, 3,148,187, 2,895,955 and 3,423,207, in CA 56 114571 and J.Org.Chem., Vol 42,1977, page 885. Synthetic techniques are also described by Y.L.Slominskii et al, UKR. Khim.
  • the infrared sensitizing dyes used in the present invention spectrally sensitize silver halide emulsions to radiation in the infrared from 700 nm upwards, especially from 750 to 850 nm, to provide photographic elements which are particularly suitable with a number of commercially available laser diodes.
  • the sensitizing dyes used in this invention exhibit an increased stability of their solutions during keeping.
  • the infrared sensitizing dyes used in the present invention are incorporated in the silver halide photographic emulsion layer in a content of 5x10 ⁇ 7 mol to 5x10 ⁇ 3 mol, preferably 1x10 ⁇ 6 mol to 1x10 ⁇ 3 mol, more preferably 2x10 ⁇ 6 mol to 5x10 ⁇ 4 mol, per mol of silver within the particular layer which is being sensitized by that dye.
  • a silver halide photographic element comprising a support, at least one infrared sensitive silver halide emulsion layer and at least one hydrophilic colloid non photosensitive layer, wherein at least one infrared sensitive silver halide emulsion layer contains an infrared sensitizing dye and a stabilizing amount of an organic reducing agent and of an alkaline buffering agent.
  • silver halide photographic materials include black-and-white and color photographic elements.
  • Infrared sensitive silver halide color photographic elements for use in the present invention are preferably those described in US Pat. No. 4,619,892, which is incorporated herein by reference. More preferably, the infrared sensitive silver halide color photographic elements for use in the present invention are those having all of the silver halide emulsion layers sensitized to different infrared regions of the electromagnetic spectrum. The order of these layers respect to the support, the difference in emulsion sensitivity among the layers and the sensitivity, contrast and D-max of each layer are preferably those described in said US Pat. No. 4,619,892.
  • the dyes used in the present invention find particular utility when used for spectrally sensitizing to infrared radiation a silver halide emulsion layer in photographic elements that include at least one other infrared-sensitive silver halide layer.
  • Preferred examples of said photographic elements are those comprising at least three silver halide emulsion layers on a substrate, each associated with different photographic colour image forming materials such as color couplers capable of forming dyes of different colors upon reaction with an oxidised color photographic developer, diffusing dyes, bleachable dyes or oxidizable leuco dyes, the three emulsion layers being sensitized to three different portions of the visible spectrum with at least one layer, preferably at least two layers, sensitized to radiation within the infrared region of the spectrum.
  • silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and mixtures thereof may be used, for example, dispersed in a hydrophilic colloid or carrier.
  • the silver halide grains in the photographic emulsion may be regular grains having a regular crystal structure such as cube, octahedron, and tetradecahedron, or the spherical or irregular crystal structure, or those having crystal defects such as twin plane, or those having a tabular form, or the combination thereof.
  • the photographic element comprising a layer including the dyes of this invention may be coated on any suitable support material used in photography such as cellulose acetate, cellulose nitrate, paper, polyesters, such as polyethylene terephthalate, etc.
  • gelatin is advantageously used, but other hydrophilic colloid may be used alone or in combination with gelatin such as gelatin substitutes, collodion, gum arabic, cellulose ester derivatives such as alkyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, synthetic resins, such as the amphoteric copolymers described in US Pat. No. 2,949,442, polyvinyl alcohol, and others well known in the art.
  • the colloid may be partially hardened or fully hardened by any of the variously known photographic hardeners.
  • Such hardeners are free aldehydes, aldehyde releasing compounds, triazines and diazines, aziridines, vinylsulfones, carbodiimides, and the like may be used, as described, for example, in US Pat. Nos. 3,232,764, 2,870,013, 3,819,608, 3,325,287, 3,992,366, 3,271,175 and 3,490,911.
  • the silver halide photographic elements can be used to form dye images therein through the selective formation of dyes.
  • the photographic elements described above for forming silver images can be used to form dye images by employing developers containing dye image formers, such as color couplers, as described, for example, in US Pat. Nos. 3,111,864, 3,002,836, 2,271,238, 2,236,598, 2,950,970, 2,592,243, 2,343,703, 2,376,380, 2,369,489, 2,899,306, 3,152,896, 2,115,394, 2,252,718, 2,108,602, and 3,547,650.
  • dye image formers such as color couplers
  • the developer contains a color developing agent (e.g., a primary aromatic amine which in its oxidized form is capable of reacting with the coupler to form the image dye).
  • a color developing agent e.g., a primary aromatic amine which in its oxidized form is capable of reacting with the coupler to form the image dye.
  • instant self-developing diffusion transfer film can be used as well as photothermographic color film or paper using silver halide in catalytic proximity to reducable silver sources and leuco dyes.
  • the dye-forming couplers can be incorporated in the photographic elements, as illustrated by Schneider et al., Die Chemie , Vol. 57, 1944, p. 113, and in US Pat. Nos. 2,304,940, 2,269,158, 2,322,027, 2,376,679, 2,801,171, 2,748,141, 2,772,163, 2,835,579, 2,533,514, 2,353,754, 3,409,435 and Chen, Research Disclosure, Vol. 159, July 1977, Item 15930.
  • the dye-forming couplers can be incorporated in different amounts to achieve differing photographic effects.
  • GB Pat. No. 923,045 and US Pat. No. 3,843,369 teach limiting the concentration of coupler in relation to the silver coverage to less than normally employed amounts in faster and intermediate speed emulsion layers.
  • the dye-forming couplers are commonly chosen to form subtractive primary (i.e., yellow, magenta and cyan) image dyes and are nondiffusible, colorless couplers, such as two and four equivalent couplers of the open chain ketomethylene, pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, phenol and naphthol type hydrophobically ballasted for incorporation in high-boiling organic (coupler) solvents.
  • Such couplers are illustrated in US Pat. Nos.
  • the dye-forming couplers upon coupling can release photo-graphically useful fragments, such as development inhibitors or accelerators, bleach accelerators, developing agents, silver halide solvents, toners, hardeners, fogging agents, antifoggants, competing couplers, chemical or spectral sensitizers and desensitizers.
  • Development inhibitor-releasing (DIR) couplers are illustrated in US Pat. Nos. 3,148,062, 3,227,554, 3,733,201, 3,617,291, 3,703,375, 3,615,506, 3,265,506, 3,620,745, 3,632,345, 3,869,291, 3,642,485, 3,770,436, 3,808,945, and in GB Pat. Nos. 1,201,110 and 1,236,767.
  • Dye-forming couplers and nondye-forming compounds which upon coupling release a variety of photographically useful groups are described in US Pat. No. 4,248,962.
  • DIR compounds which do not form dye upon reaction with oxidized color developing agents can be employed, as illustrated in US Pat. Nos. 3,928,041, 3,958,993, 3,961,959, 4,049,455, 4,052,213 and in German OLS Nos. 2,529,350, 2,448,063 and 2,610,546.
  • DIR compounds which oxidatively cleave can be employed, as illustrated in US Pat. Nos. 3,379,529, 3,043,690, 3,364,022, 3,297,445 and 3,287,129.
  • Silver halide emulsions which are relatively light insensitive, such as Lippmann emulsions, having been used as interlayers or overcoat layers to prevent or control the migration of development inhibitor fragments as described in US Pat. No. 3,892,572 can be employed.
  • the photographic elements can incorporate colored dye-forming couplers, such as those employed to form integral masks for negative color images, as illustrated in US Pat. Nos. 2,449,966, 2,521,908, 3,034,892, 3,476,563, 3,519,429, 2,543,691, 3,028,238, 3,061,432, and/or competing couplers, as illustrated in US Pat. Nos. 3,876,428, 3,580,722, 2,998,314, 2,808,329, 2,742,832 and 2,689,793.
  • colored dye-forming couplers such as those employed to form integral masks for negative color images, as illustrated in US Pat. Nos. 2,449,966, 2,521,908, 3,034,892, 3,476,563, 3,519,429, 2,543,691, 3,028,238, 3,061,432, and/or competing couplers, as illustrated in US Pat. Nos. 3,876,428, 3,580,722, 2,998,314, 2,808,329, 2,742,832 and 2,689,793.
  • the color provided in the image produced by exposure of each of the differently sensitized silver halide emulsion layers does not have to be produced by color coupler reaction with oxidized color developers.
  • a number of other color image forming mechanisms well known in the art can also be used.
  • the commercially available color image forming mechanisms are the diffusion transfer of dyes, dye-bleaching, and leuco dye oxidation. Each of these procedures is used in commercial products, is well understood by the ordinary skilled photographic artisan, and is used with silver halide emulsions. Multicolor elements using these different technologies are also commercially available.
  • the photographic elements can include image dye stabilizers.
  • image dye stabilizers are illustrated in US Pat. Nos. 3,432,300, 3,698,909, 3,574,627, 3,573,050, 3,764,337, and 4,042,394 and in GB Pat. No. 1,326,889.
  • Filter dyes can be included in the photographic elements. Said dyes must be selected on the basis of their radiation filtering characteristics to insure that they filter the appropriate wavelengths. Filter dyes and their methods of incorporation into the photographic elements are well documented in the literature such as US Pat. Nos. 4,440,852, 3,671,648, 3,423,207, and 2,895,955, GB Pat. No. 485,624, and Research Disclosure, Vol. 176, December 1978, Item 17643. Filter dyes can be used in the practice of the present invention to provide room-light handleability to the elements.
  • Dyes which will not allow transmission of radiation having wavelengths shorter than the shortest wavelength to which one of the emulsion layers has been sensitized can be used in a layer above one or more (preferably all) of the emulsion layers.
  • the cut-off filter dye preferably does not transmit light more than approximately 50 nm less than the shortest wavelength to which any of the emulsion layers have been sensitized.
  • Filter dyes should also be provided with non-fugitive (i.e., non-migratory) characteristics and should be decolorizable (by bleaching in developer or heat, for example) or leachable (e.g., removed by solvent action of any baths).
  • photographic addenda such as coating aids, antistatic agents, acutance dyes, antihalation dyes and layers, antifoggants, latent image stabilizers, supersentizers, antikinking agents, high intensity reciprocity failure reducers, and the like may also be present.
  • spectral sensitizing Dye 4 0.1 g were dissolved in 10 ml of 2-phenoxyethanol, the resulting solution was made up to 100 ml with methanol at 20°C.
  • the methanolic solution contained 100 mg of ascorbic acid and 250 mg of sodium acetate.
  • the methanolic solution contained 200 mg of ascorbic acid and 250 mg of sodium acetate.
  • the methanolic solution contained 50 mg of ascorbic acid and 250 mg of sodium acetate.
  • the methanolic solution contained 30 mg of ascorbic acid and 250 mg of sodium acetate.
  • the methanolic solution contained 100 mg of ascorbic acid and 150 mg of sodium acetate.
  • the methanolic solution contained 100 mg of ascorbic acid and 350 mg of sodium acetate.
  • a solution can be considered stable if the value obtained is at least 90%, preferably at least 95% of the initial value, without any precipitation of the solution that renders it not useful for the incorporation in a silver halide photographic material.
  • Table 1 shows that samples 4-9 are useful in the present invention.
  • Table 2 reports the stability data measured as in Example 1.
  • Table 2 Sample Percentage after 48 hours 10 (ref.) 79% 11 (ref.) 96% 12 (ref.) 89% 13 (ref.) 99%
  • the fresh prepared solution of spectral sensitizing Dye 16 contained also 0.1% of ascorbic acid and 0.25% of sodium acetate.
  • the films were exposed to an EDG sensitometer with a neutral density filter and a Wratten R 87 filter (manufactured by Eastman Kodak Co.) through a standard step-wedge and developed for 27 seconds at 35°C in a 3M XAD/2 developer, fixed for 27 seconds at 30°C, washed with tap water for 22 seconds at 35°C and dried for 22 seconds at 35°C in a TrimaticTM XP 515 roller transport processor.
  • the sensitometric results in terms of Dmin and Speed are reported in Table 3. Speed values are expressed in Log E (where E represents exposure in meter-candle-seconds, measured at a density of 1.0 above Dmin). Table 3 Film Dmin Speed 1 (ref.) 0.17 1.85 2 (inv.) 0.17 2.28
  • Table 3 shows that the film No. 2 of the present invention, containing a fresh prepared solution of spectral sensitizing dye stabilized by ascorbic acid and by sodium acetate presented a relevant speed improvement, still maintaining the same value of Dmin, compared to the reference sample, wherein the fresh prepared solution of spectral sensitizing dye has not been stabilized.
  • the speed improvement of Film 2 is greater if the solution of spectral sensitizing dye is added to the silver halide emulsion after being kept on shelf life for at least 48 hours, compared with the speed of the reference film 1 using a non-stabilized solution of spectral sensitizing dye added to the silver halide emulsion after 48 hours storage.
  • the composition was coated onto a conventional photographic paper base at a silver coverage of 0.28 g/m2.
  • the photosensitive layer was overcoated with a protective layer comprising gelatin, a surfactant and a bis-vinylsulfonyl type hardener.
  • the fresh prepared solution of spectral sensitizing Dye 4 also contained 0.10% of ascorbic acid and 0.25% of sodium acetate.
  • each film was exposed to a laser diode at 820 nm.
  • the exposed coatings were developed in a Kodak RA-4 processing line.
  • Table 4 shows the sensitometric results in terms of Dmin and Speed.
  • Table 4 Film Dmin Speed 3 (ref.) 0.17 2.70 4 (inv.) 0.17 2.74
  • Table 4 shows that the film No. 4 of the present invention, containing a fresh prepared solution of spectral sensitizing dye stabilized by ascorbic acid and by sodium acetate presented a little speed improvement, still maintaining the same value of Dmin. As in Example 3, more relevant speed improvement can be obtained if the solutions of spectral sensitizing dyes are added after at least 48 hours from their preparation.

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EP94101874A 1994-02-08 1994-02-08 Photographische, Infrarot-sensibilisierende farbstoffenthaltende Silberhalogenidelemente Ceased EP0666496A1 (de)

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EP94101874A EP0666496A1 (de) 1994-02-08 1994-02-08 Photographische, Infrarot-sensibilisierende farbstoffenthaltende Silberhalogenidelemente
JP1904395A JPH07230139A (ja) 1994-02-08 1995-02-07 赤外増感色素を含むハロゲン化銀写真エレメント

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DE19815357A1 (de) * 1998-04-06 1999-10-07 Maidhof Vertriebs Gmbh & Co Kg Warenverkaufsautomat
JP4577873B2 (ja) * 2004-04-09 2010-11-10 旭化成ファーマ株式会社 試薬の安定性を改善する方法

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US3695888A (en) * 1970-05-28 1972-10-03 Eastman Kodak Co Photographic supersensitized silver halide emulsions
US3753721A (en) * 1970-08-13 1973-08-21 Eastman Kodak Co Photographic materials
JPS5175432A (ja) * 1974-12-25 1976-06-30 Fuji Photo Film Co Ltd Hozonseigakairyosaretashikisonosuiseiyoeki
JPS61290441A (ja) * 1985-06-18 1986-12-20 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真乳剤の製造方法
JPS62215261A (ja) * 1986-03-15 1987-09-21 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
US4897343A (en) * 1987-05-13 1990-01-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4917997A (en) * 1987-09-11 1990-04-17 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5037734A (en) * 1989-12-28 1991-08-06 Eastman Kodak Company Stabilized photographic element containing infrared sensitizing dye
EP0568850A1 (de) * 1992-05-06 1993-11-10 E.I. Du Pont De Nemours And Company Photographische Silberhalogenidsysteme enthaltend wasserlösliche Cyclodextrin-Adjuvans-Addukte

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Publication number Priority date Publication date Assignee Title
US3695888A (en) * 1970-05-28 1972-10-03 Eastman Kodak Co Photographic supersensitized silver halide emulsions
US3753721A (en) * 1970-08-13 1973-08-21 Eastman Kodak Co Photographic materials
JPS5175432A (ja) * 1974-12-25 1976-06-30 Fuji Photo Film Co Ltd Hozonseigakairyosaretashikisonosuiseiyoeki
JPS61290441A (ja) * 1985-06-18 1986-12-20 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真乳剤の製造方法
JPS62215261A (ja) * 1986-03-15 1987-09-21 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
US4897343A (en) * 1987-05-13 1990-01-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4917997A (en) * 1987-09-11 1990-04-17 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5037734A (en) * 1989-12-28 1991-08-06 Eastman Kodak Company Stabilized photographic element containing infrared sensitizing dye
EP0568850A1 (de) * 1992-05-06 1993-11-10 E.I. Du Pont De Nemours And Company Photographische Silberhalogenidsysteme enthaltend wasserlösliche Cyclodextrin-Adjuvans-Addukte

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Title
DATABASE WPI Section PQ Week 7633, Derwent World Patents Index; Class P83, AN 76-62327X *
G HAIST: "MODERNOHOTOGRAPHIC PROCESSING VOLUME 1", 1979, JOHN WILEY AND SONS, NEW YORK *
PATENT ABSTRACTS OF JAPAN vol. 11, no. 156 (P - 578)<2603> 21 May 1987 (1987-05-21) *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 76 (P - 675)<2923> 10 March 1988 (1988-03-10) *

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