EP0398600B1 - Empfindlichkeits- und kontrastgesteigerte dotierte Silberhalogenidemulsionen - Google Patents

Empfindlichkeits- und kontrastgesteigerte dotierte Silberhalogenidemulsionen Download PDF

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Publication number
EP0398600B1
EP0398600B1 EP90305114A EP90305114A EP0398600B1 EP 0398600 B1 EP0398600 B1 EP 0398600B1 EP 90305114 A EP90305114 A EP 90305114A EP 90305114 A EP90305114 A EP 90305114A EP 0398600 B1 EP0398600 B1 EP 0398600B1
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Prior art keywords
emulsion
silver halide
speed
moieties
photographic element
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP90305114A
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English (en)
French (fr)
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EP0398600A2 (de
EP0398600A3 (de
Inventor
Steven Michael C/O Building 209-2C-08 Shor
Kevin Peter 5 Blacksmiths Way Hall
Sean Dennis 16 Old School Close Slater
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3M Co
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Minnesota Mining and Manufacturing Co
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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
    • G03C1/10—Organic 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
    • G03C1/067—Additives for high contrast images, other than hydrazine compounds
    • 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
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers

Definitions

  • This invention relates to negative-acting silver halide photographic materials and in particular to photographic elements comprising Group VIII metal doped silver halide emulsions associated with a speed and contrast promoting agent which are suitable for use in the photolithographic printing industry and for the development of daylight handleable contact film.
  • Photosensitive silver halide materials are commonly used in the photolithographic industry to obtain half tone, dot or line, high contrast images.
  • contrast promoting agents among which are the water soluble Group VIII metal salts, such as the trivalent salts of rhodium, ruthenium and iridium. It is known that good results as regards high covering power (which is the ratio between the maximum density obtained after development and the silver halide coverage) and rapid developability (for productivity increase) can be obtained by using fine grained (less than 0.15 ⁇ m) and high chloride content silver halide emulsions. It is known that such emulsions which contain a Group VIII metal as a contrast promoting agent may still not have the required contrast, and as the dopant desensitises the emulsion, it may not have the required speed.
  • contrast promoting agents among which are the water soluble Group VIII metal salts, such as the trivalent salts of rhodium, ruthenium and iridium.
  • British Patent No. 741228 discloses the use of 4-substituted 3-amino-5-mercapto-4,1,2-triazoles of general formula (I) in which: R represents other than H, in photographic constructions.
  • the compounds of formula (I) are said to restrain the formation of chemical fog without seriously affecting the speed, contrast or other properties of the emulsion.
  • U.S. Patent No. 1,725,934 discloses the use of thiazole derivatives in silver halide constructions, but as an anti-fogging agent.
  • DE-A-3403825 discloses a photographic material comprising a support and photographic layers including at least one silver halide emulsion layer which comprises (1) spectrally unsensitised negative silver halide having an average grain size of 0.1 to 0.3 ⁇ m and containing 80 mole % or more of silver chloride and (2) an organic desensitiser having an anodic polarographic potential and a cathodic polarographic potential which give a positive sum, and said photosensitive material meets at least one of the following requirements:
  • JP-59-79250 discloses a silver halide photosensitive material for imagewise exposure containing at least 95 mol % silver chloride prepared in the presence of from 10 -7 to 10 -2 mol rhodium salt per mole of silver halide. It is processed with a developing solution containing a compound represented by general formula I and a compound represented by general formula II or III, and as a developing agent, substantially only p-dihydroxybenzene type developing agent, and more than 0.2 mol/l sulfite ions, and a pH of at least 11.
  • DE-A-23 21 401 discloses a developer solution for the infectious development of silver halide light-sensitive material, which solution comprises a dihydroxybenzene as silver halide developing agents, an alkali, 0.005 to 0.05 mole per litre of free sulphite, a sulphite ion buffer and at least 10 milligrams per litre of the solution of a heterocyclic mercapto compound of the general formula: in which: Z represents the non-metallic atoms necessary to complete a 5- or 6-membered heterocyclic ring and comprises one or more carbon atom, nitrogen atom, sulphur atom and/or oxygen atom, the heterocyclic ring may be fused to another ring, and the ring or either or the rings may have one or more substituents; X represents a hydrogen atom, a cation or an alkyl group, and n is 1, 2 or 3.
  • a photographic element comprising negative-acting silver halide emulsion characterised by the combination of features that the silver halide is doped with from 2.3 x 10 -5 to 10 -2 moles of a Group VIII metal per mole of silver and that the emulsion is associated with one or more speed and contrast promoting agents comprising a compound having a nucleus of one of the following general formulae: (i) to (iv) in which:
  • the invention provides a negative-acting photosensitive silver halide material which may be used to obtain black and white half tone, line or dot images for photolithographic purposes.
  • the element preferably comprises a support, having one or more hydrophilic colloidal layers located thereon, in which at least one layer comprises a fine grain, high chloride content and Group VIII metal doped photographic emulsion associated with one or more speed and contrast promoting agents selected from compounds of general formulae (i) to (iv).
  • the speed and contrast promoting agents need not be present in the emulsion during imaging, but must be associated with the emulsion during development.
  • the compounds of general formulae (i) to (iv) may be introduced in to the emulsion from a treatment bath or the developer solution.
  • the compounds may be present in the photographic element during imaging and optionally additional compounds present in the developer solution.
  • Examples of compounds suitable for inclusion as speed or contrast promoting agents are:
  • the fine grain, high chloride content and Group VIII metal doped photographic emulsion is associated with one or more speed and contrast promoting agents selected from compounds A to E.
  • the material After image wise exposure of the fine grain, high chloride content rhodium doped silver halide emulsion, the material undergoes a photographic processing step comprising an alkaline developing solution wherein the speed and contrast promoting agent is reactively associated with the emulsion.
  • a photographic processing step comprising an alkaline developing solution wherein the speed and contrast promoting agent is reactively associated with the emulsion.
  • the speed and contrast promoting agent in the developer solution followed by conventional washing or fixing but it is preferred that the agents are introduced as a precoating addition.
  • fine grain is used in the context of the present invention to refer to silver halide grains having an average grain size of not more than 0.2 ⁇ m.
  • High chloride content refers to the emulsion having at least 60% and preferably at least 80% of its total halide molar content consisting of chloride ions.
  • the emulsion is preferably a chlorobromide emulsion wherein the remainder of the halide content comprises bromide ions and a most preferred emulsion comprises 84% silver chloride : 16% silver bromide having a mean silver halide grain size of 0.09 ⁇ m.
  • Group VIII metal doped refers to the process whereby during precipitation or physical ripening of the silver halide emulsion, salts of one or more Group VIII metals, e.g., trisodium hexachlororhodate (III), disodium pentachlororuthenate (III) and tripotassium hexachloroiridate (III) are present in the solution.
  • the preferred dopants are water-soluble trivalent salts of rhodium.
  • the speed and contrast increasing effect of the compounds of general formulae (i) to (iv) is directly proportional to the level of dopant.
  • the level of doping may be 2.3 x 10 -5 to 10 -2 moles Group VIII metal salt per mole of silver, preferably 10 -4 to 10 -2 moles Group VIII metal salt per mole of silver and most preferably from 10 -3 to 10 -2 mole Group VIII metal salt per mole of silver.
  • the amount of the speed and contrast promoting agent added is in the range 10 -4 to 10 -1 mole of agent per mole of silver halide but preferably in the range 10 -2 to 5 x 10 -2 mole of agent per mole of silver halide.
  • a silver halide emulsion of 84 mole % chloride and 16 mole % bromide was prepared by the simultaneous addition under constant agitation of water solution B and water Solution C by the double jet technique over a period of 25 minutes to water gelatin Solution A.
  • the compositions A to C were:
  • the water gelatin Solution A was kept at a constant temperature of 40°C.
  • Solution B was added at a constant addition rate whilst the addition rate of Solution C was varied to maintain the potential of the emulsion thus formed at a value of 120 ⁇ 5mV (as measured with a specific electrode for Br ions and a reference electrode of the saturated Ag/AgC1 type).
  • the emulsion so prepared following the removal of soluble salts by the conventional coagulation method, had a mean grain diameter of 0.09 ⁇ m.
  • the emulsion was then chemically sensitised with sodium gold chloride and sodium thiosulphate. At the end of the chemical sensitisation a speed and contrast promoting agent selected from compounds A to J in a suitable solvent was added to the emulsion before preparation for coating with the addition of additional gelatin, coating surface active agents and formaldehyde hardener.
  • the emulsion was coated at a silver coating weight of 2.7g Ag/m 2 onto a polyester support base which was backed with a red antihalation layer.
  • the resulting films were exposed through a 0-2, 20cm continuous wedge.
  • the exposing lamp was a Violux 1500S UV lamp at a distance of 52 inches from the film plane.
  • the exposed films were developed in 3M RDC TM developer for 20 seconds @ 40°C and fixed in 3M Fix Roll TM Fixer.
  • Contrast A is measured between densities 0.07 and 0.17 above Dmin.
  • Contrast C is measured between densities 0.5 and 2.5 above Dmin.
  • Each of compounds A to F were dissolved in an appropriate solvent and added at varying levels as a precoating addition to the emulsion.
  • the emulsion used had the composition described previously and had been chemically sensitised with conventional sulphur and gold compounds.
  • no speed and contrast enhancing compound is added and with conventional exposure and processing the film shows little development, only on extremely long exposures to UV light does any density build up.
  • the compounds of the invention are added, then a dramatic speed and contrast increase is seen.
  • Example 2 An alternative to the emulsion composition described in Example 1 was tested with Compound A.
  • the emulsion was made following the protocol described previously except the halide ratio was altered from 84 : 16 chloride to bromide to 96 : 4. Very similar results were observed with increases in both speed and contrast.
  • digested emulsion composition as per Example 1
  • the film was given the standard exposure and processed in RDC developer having some of compound A added. Washing and fixing were carried out in a conventional fashion.
  • Emulsion 4 was found to be too fast to be exposed by the Violux UV lamp so exposure was conducted with a quartz lamp.
  • Table 6 shows the increase in speed (logE) observed on chemical sensitisation when Compound A is added as a precoating addition or not added at all. It can be seen that with no Compound A present, digestion gives a greater increase in speed with increasing levels of rhodium dopant, when Compound A is added as a final the effect of chemical sensitisation decreases with increasing rhodium dopant level i.e. at higher rhodium levels most of the speed increase comes from the addition of Compound A, the digestion step only gives a small further speed increase.
  • Example 2 An emulsion similar to that in Example 1 was prepared except that the halide ratio was adjusted so that it was 96 mole % chloride 4% bromide emulsion. Seven emulsions were prepared with the following levels of Group VIII transition metal dopants.
  • Example 2 Once prepared the emulsion was washed and chemically sensitised in the same way as in Example 1. Compound A was then added at a level of 1.95g per mole of silver. The emulsion was then coated onto clear subbed polyester with the conventional coating aids and hardeners at a coating weight of 2.5g Ag/m 2 .
  • the resulting films were exposed through a 0-4 10cm continuous wedge.
  • the exposing source was a Thiemer Spektra Proof Daylight containing a 1KW Th1007 polymer bulb.
  • the exposed films were developed in 3M RDC developer for 30 seconds at 35°C and fixed in 3M Fix Roll fixer.
  • Emulsions 6 and 7 show the effect of iridium doping. There is an overall desensitisation related to the level of dopant (see li) 6i) and 7i). On addition of Compound A speed, contrast and for the heavily doped emulsion maximum density are increased. For Emulsion 7 solarisation is also observed which is eliminated on addition of Compound A.

Claims (12)

  1. Photographisches Element, umfassend eine negativ wirkende Silberhalogenidemulsion, gekennzeichnet durch die Kombination von Merkmalen, daß das Silberhalogenid mit von 2,3 x 10-5 bis 10-2 Mol eines Metalls der Gruppe VIII pro Mol Silber dotiert ist und daß die Emulsion mit einem oder mehreren die Empfindlichkeit und den Kontrast fördernden Mitteln verbunden ist, die eine Verbindung umfassen, die einen Kern einer der allgemeinen Formeln (i) bis (iv) besitzt:
    Figure imgb0026
    Figure imgb0027
     in denen:
    jedes R1, unabhängig, ein Wasserstoffatom oder einen Alkylrest mit 1 bis 5 Kohlenstoffatomen bedeutet, der gegebenenfalls ein oder mehrere Substituenten, ausgewählt aus Hydroxygruppen, Carboxygruppen, Alkoxycarbonylresten mit 1 bis 5 Kohlenstoffatomen, Cyanogruppen, Halogenatomen, Nitrogruppen, Aminogruppen und Arylresten mit bis zu 10 Kohlenstoffatomen, besitzt, wobei der Arylrest gegebenenfalls mit einem oder mehreren Substituenten, ausgewählt aus Alkylresten mit 1 bis 5 Kohlenstoffatomen, Hydroxygruppen, Carboxygruppen, Alkoxycarbonylresten mit 1 bis 5 Kohlenstoffatomen, Cyanogruppen, Halogenatomen, Nitrogruppen und Aminogruppen, substituiert sein kann,
    X1 N oder CR5 bedeutet, wobei R5 R1 (wie vorstehend definiert) oder NO2 bedeutet.
    R2 ein Wasserstoffatom oder SR1 (wobei R1 die vorstehende Definition besitzt), bedeutet, aber falls X1 N ist, R2 dann SR1 bedeutet,
    Q S oder NR1 bedeutet, wobei R1 wie vorstehend definiert ist,
    R3 eine Aminogruppe oder SR1 bedeutet, wobei R1 wie vorstehend definiert ist, und
    jedes R4, unabhängig, R1, wie vorstehend definiert, oder ein Halogenatom, eine Nitrogruppe, eine Cyanogruppe oder einen Alkoxycarbonylrest mit 1 bis 5 Kohlenstoffatomen bedeutet, und die Emulsion frei von Hydrazinderivaten ist.
  2. Photographisches Element nach Anspruch 1, dadurch gekennzeichnet, daß das Metall der Gruppe VIII als Dotierungsmittel Rhodium ist.
  3. Photographisches Element nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das die Empfindlichkeit und den Kontrast fördernde Mittel eine Verbindung ausgewählt aus
    Figure imgb0028
    Figure imgb0029
     und
    Figure imgb0030
     ist.
  4. Photographisches Element nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Silberhalogenidemulsion einen Träger umfaßt, auf den eine oder mehrere hydrophile, kolloidale Schichten aufgetragen sind, wobei mindestens eine Schicht eine Silberhalogenidemulsion mit feinem Korn umfaßt, das eine durchschnittliche Korngröße von nicht größer als 0,2 µm besitzt.
  5. Photographisches Element nach Anspruch 4, dadurch gekennzeichnet, daß die Silberhalogenidemulsion eine Chlorbromidemulsion umfaßt, in der Silberchlorid mindestens 60% des gesamten Silbergehalts umfaßt.
  6. Photographisches Element nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das die Empfindlichkeit und den Kontrast fördernde Mittel eine Konzentration von 10-4 bis 10-1 Mol pro Mol Silberhalogenid besitzt.
  7. Photographisches Element nach einem der vorstehenden Ansporüche, dadurch gekennzeichnet, daß die Konzentration des Metalls der Gruppe VIII als Dotierungsmittel von 10-4 bis 10-2 Mol Dotierungsmittel pro Mol Silberhalogenid beträgt.
  8. Photographisches Element nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Dotierungsmittel ein in Wasser lösliches dreiwertiges Rhodiumsalz umfaßt.
  9. Photographisches Element nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Silberhalogenidemulsion mit Schwefel und Gold sensibilisiert ist.
  10. Photographisches Verfahren, umfassend das bildweise Belichten eines photographischen Elements, umfassend eine negativ wirkende Silberhalogenidemulsion, die mit von 2,3 x 10-5 bis 10-2 Mol eines Metalls der Gruppe VIII pro Mol Silber dotiert ist, wobei die Emulsion frei von Hydrazinderivaten ist, Entwickeln und Fixieren des belichteten Elements, in dem während der Entwicklung ein oder mehrere die Empfindlichkeit und den Kontrast fördernde Mittel mit der Emulsion verbunden sind, und wobei das Mittel aus Verbindungen ausgewählt ist, die einen Kern der allgemeinen Formeln besitzen:
    Figure imgb0031
    Figure imgb0032
     wobei:
       R1 bis R4, X1 und Q wie im Anspruch 1 definiert sind, mit der Maßgabe, daß die Entwicklerlösung nicht für eine infectiöse Entwicklung des lichtempfindlichen Silberhalogenidmaterials geeignet ist.
  11. Photographisches Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß das die Empfindlichkeit und den Kontrast fördernde Mittel:
    (i) in der Emulsion vor dem Belichten vorhanden ist, und/oder
    (ii) nach dem Belichten in die Emulsion eingemischt wird, und/oder
    (iii) in der Entwicklerlösung vorhanden ist.
  12. Entwicklerlösung für ein photographisches Element, dadurch gekennzeichnet, daß die Entwicklerlösung ein oder mehrere die Empfindlichkeit und den Kontrast fördernde Mittel der Formel:
    Figure imgb0033
    Figure imgb0034
     umfaßt, in denen:
    R1 bis R4, X1 und Q wie im Anspruch 1 definiert sind, mit der Maßgabe, daß die Entwicklerlösung nicht für eine infectiöse Entwicklung des lichtempfindlichen Silberhalogenidmaterials geeignet ist.
EP90305114A 1989-05-18 1990-05-11 Empfindlichkeits- und kontrastgesteigerte dotierte Silberhalogenidemulsionen Expired - Lifetime EP0398600B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8911453 1989-05-18
GB898911453A GB8911453D0 (en) 1989-05-18 1989-05-18 Speed and contrast promoted silver halide rhodium doped emulsions

Publications (3)

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EP0398600A2 EP0398600A2 (de) 1990-11-22
EP0398600A3 EP0398600A3 (de) 1991-10-09
EP0398600B1 true EP0398600B1 (de) 1996-10-09

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EP (1) EP0398600B1 (de)
JP (1) JPH036551A (de)
AU (1) AU624946B2 (de)
CA (1) CA2016495A1 (de)
DE (1) DE69028801T2 (de)
GB (1) GB8911453D0 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8329914B2 (en) 2008-10-31 2012-12-11 Merck Sharp & Dohme Corp Cyclic benzimidazole derivatives useful as anti-diabetic agents
US8563746B2 (en) 2008-10-29 2013-10-22 Merck Sharp & Dohme Corp Cyclic benzimidazole derivatives useful as anti-diabetic agents

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR9912098A (pt) 1998-07-15 2001-09-25 Teijin Ltd Derivado de tiobenzimidazol, composição farmacêutica, e, agente preventivo e/ou terapêutico

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2321401A1 (de) * 1972-04-28 1973-11-15 Fuji Photo Film Co Ltd Entwicklungsverfahren und entwicklungsbad

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3403825A1 (de) * 1983-02-04 1984-08-16 Mitsubishi Paper Mills, Ltd., Tokyo Fotografische, fotoempfindliche silberhalogenidmaterialien
GB2190510B (en) * 1986-04-02 1989-11-22 Fuji Photo Film Co Ltd Silver halide photographic material and image-forming method using the same
JPH0612406B2 (ja) * 1986-11-14 1994-02-16 富士写真フイルム株式会社 超硬調ネガ型ハロゲン化銀写真感光材料
JPH01183643A (ja) * 1988-01-18 1989-07-21 Fuji Photo Film Co Ltd ハロゲン化銀カラー感光材料

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2321401A1 (de) * 1972-04-28 1973-11-15 Fuji Photo Film Co Ltd Entwicklungsverfahren und entwicklungsbad

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8563746B2 (en) 2008-10-29 2013-10-22 Merck Sharp & Dohme Corp Cyclic benzimidazole derivatives useful as anti-diabetic agents
US8329914B2 (en) 2008-10-31 2012-12-11 Merck Sharp & Dohme Corp Cyclic benzimidazole derivatives useful as anti-diabetic agents

Also Published As

Publication number Publication date
AU624946B2 (en) 1992-06-25
EP0398600A2 (de) 1990-11-22
CA2016495A1 (en) 1990-11-18
AU5463290A (en) 1990-11-22
DE69028801D1 (de) 1996-11-14
GB8911453D0 (en) 1989-07-05
JPH036551A (ja) 1991-01-14
DE69028801T2 (de) 1997-04-10
EP0398600A3 (de) 1991-10-09

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