EP0223883B1 - Méthode pour le développement d'un matériau photographique à base d'émulsions à l'halogénure d'argent exposé - Google Patents

Méthode pour le développement d'un matériau photographique à base d'émulsions à l'halogénure d'argent exposé Download PDF

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Publication number
EP0223883B1
EP0223883B1 EP19850201959 EP85201959A EP0223883B1 EP 0223883 B1 EP0223883 B1 EP 0223883B1 EP 19850201959 EP19850201959 EP 19850201959 EP 85201959 A EP85201959 A EP 85201959A EP 0223883 B1 EP0223883 B1 EP 0223883B1
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EP
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Prior art keywords
mercapto
compound
liquid
heterocyclic
surface active
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Expired
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EP19850201959
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German (de)
English (en)
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EP0223883A1 (fr
Inventor
Antoine Roberta Van Rossen
André Cornelius Roefs
Robert Joseph Pollet
Etienne Adrianus Van Thillo
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP19850201959 priority Critical patent/EP0223883B1/fr
Priority to DE8585201959T priority patent/DE3568377D1/de
Priority to JP61280531A priority patent/JPH07119972B2/ja
Publication of EP0223883A1 publication Critical patent/EP0223883A1/fr
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents

Definitions

  • the present invention relates to a method for developing an exposed photographic silver halide emulsion material and a liquid used therein by means of which the formation of silver sludge is effectively reduced.
  • finely divided metallic silver so-called silver sludge
  • the formation of silver sludge is particularly disturbing in automatic processing apparatus wherein it results in deposits of black silver on conveyor and transport rollers and smudging of photographic material conducted therewith.
  • the emulsion layer may contain auxiliary coating agents such as saponin, sodium lauryl sulphate, dodecylphenol polyethylene oxide ether and hexadecyltrimethyl ammonium bromide.
  • a method for developing an exposed photographic silver halide emulsion material comprises the treating of said material with an aqueous alkaline liquid in the presence of (i) a developing agent, (ii) a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and (iii) a surface active agent, characterized in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant, and the mercapto compound is a heterocyclic mercapto compound corresponding to the following tautomeric general formulae (A) and (B): wherein:
  • the said anionic surfactant is preferably an alkylphenoxy(ethyleneoxy) n phosphoric acid mono- and/or di-ester compound in salt form, e.g. sodium salt, wherein n is a positive integer of at least 4, e.g. n is 4 to 25, and the alkyl group is a C8 to C20 alkyl group.
  • Heterocyclic mercapto-compounds that are within the scope of said general formulae (A) and (B) belong e.g. to the classes of mercapto-tetrazoles, mercapto-triazoles, mercapto-thiadiazoles, mercapto-oxadiazoles, mercapto-benzimidazoles, mercapto-benzoxazoles and mercapto-benzthiazoles.
  • Preferred mercapto-tetrazoles correspond to the following general formula: wherein:
  • Compound 12 of the above Table 2 can be prepared starting from n-hexadecylisothiocyanate and sodium azide in a mixture of dioxan and water.
  • Compounds 13 and 14 of the above Table 2 can be prepared by a condensation reaction using the corresponding amino-phenyl-5-mercapto-tetrazole compounds and acid chlorides.
  • alkylphenoxy polyoxyalkylene phosphoric acid mono- and/or diester surfactants The preparation of anionic alkylphenoxy polyoxyalkylene phosphoric acid mono- and/or diester surfactants is described e.g. in the book Anionic Surfactants, part II, edited by Warner M. Linfield, Marcel Dekker Inc. - New York and Basel, 509-511 (1976).
  • Alkylphenoxy polyalkyleneoxy mono- and diester phosphates are commercially available under the trade name GAFAC, e.g. GAFAC RM-710, of Antara Chemicals-General Aniline & Film Corporation, New York - USA (see Chem. Eng. News 40 (1962) No. 16, p. 87).
  • the liquid according to the present invention for use in the development of a photo-exposed photographic silver halide emulsion material is an aqueous alkaline liquid containing a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and a surface active agent, characterized in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant, and the mercapto compound is a heterocyclic mercapto compound corresponding to the following tautomeric general formulae (A) and (B): wherein:
  • Said liquid used for the development of a photo-exposed photographic silver halide emulsion material does not necessarily contain a developing agent before its use since the developing agent(s) may be present already in the photographic material. In that case the liquid is called an activator liquid.
  • the mercapto compound (ii) is present preferably in an amount of from 10- 4 to 10- 3 mole per liter and the surface active agent (iii) is present in said liquid preferably in an amount of 50 mg to 200 mg per liter.
  • the surfactant (iii) is applied in the photographic material in a water-permeable layer wherefrom it can diffuse into the developing liquid.
  • the surface active agent (iii) is present in a hydrophilic colloid layer of the photographic material at the rear side of its support with respect to the photographic silver halide emulsion layer(s), e.g. in an anti-curl or anti-halation layer.
  • a suitable coverage of surface active agent (iii) in the photographic material is e.g. in the range of 0.01 to 0.20 g per m 2 .
  • the developer liquid may contain any type of developing agent known for use in the development of exposed photographic silver halide.
  • developer compounds may be utilized hydroquinone, p-methylaminophenol, 1-phenyl-3-pyrazolidinone, p-phenylene diamine derivatives and the like.
  • the developer may contain antioxidants such as alkali-metal sulphites, bisulphites, metasulphites or metahydrogen sulphites.
  • the developer solution can be alkalized with alkali-metal hydroxides, phosphates, borates, carbonates and the like.
  • the developer liquid or activator liquid may contain still other ingredients, e.g. metal complexing agents, an anti-fogging agent, e.g.
  • potassium bromide a benzotriazole, a benzothiazole, a tetrazole, e.g. up to 0.03 g per liter of 1-phenyl-5-mercapto-tetrazole, solvents improving the dissolution of the developing agents, e.g. alcohols, polyethylene glycols and esters thereof and alkanolamines, surface active agents other than the above mentioned compound (iii), development retarding or activating compounds, e.g. quaternary ammonium salts, and gelatin hardening agents, e.g. dialdehyde compounds such as glutardialdehyde.
  • solvents improving the dissolution of the developing agents e.g. alcohols, polyethylene glycols and esters thereof and alkanolamines
  • surface active agents other than the above mentioned compound (iii) e.g. quaternary ammonium salts
  • gelatin hardening agents e.g. dialdehyde compounds such as glutardialdeh
  • the pH of the alkaline activator or developer solution is generally in the range of 8.5 to 11.
  • the present invention includes the development by means of the above defined liquid of any type of photographic silver halide emulsion layer material, e.g. a graphic art and X-ray recording material.
  • any type of photographic silver halide emulsion layer material e.g. a graphic art and X-ray recording material.
  • the silver halide used in the silver halide emulsion layer(s) may be of any type or composition used in silver halide photography.
  • the liquid according to the present invention may be applied in the development of black-and-white materials as well as in colour development.
  • the development proceeds advantageously in conjunction with the silver halide complex diffusion transfer reversal process (DTR-process) described in detail in the already mentioned book of A.Rott and E.Weyde.
  • the development process according to the present invention is advantageously applied in automatic processing equipment containing conveyer rollers as described, e.g. in US-P 3 025 779 and 3 545 971.
  • a filter may be used wherethrough the liquid is pumped in a closed circuit.
  • a cartridge filter wherefrom the filter medium, e.g. cellulose yarn, can be removed from the filter housing and burned without leaving ashes.
  • the filter medium e.g. cellulose yarn
  • filter media comprising a mercapto-compound (ii) as defined herein intercept colloidal noble metal even when the pores of the filter medium are rather large and by their diameter are not contributing to an absolute interception.
  • the flow-through speed or pump pressure may be increased so that larger volumes of liquid can be freed from noble metal within the same period of time.
  • Photosensitive paper sheet materials containing a silver halide emulsion layer incorporating silver bromoiodide grains (containing 99 mole % of bromide) at a coverage of 2.85 g per m 2 expressed as silver nitrate were exposed through a graphic original so that about 10% of the total surface of each sheet material had been exposed.
  • These sheet materials were developed in a developer containing the following ingredients in 1000 ml of demineralized water. The development was carried out at 35 ° C in a developer tank containing 24 liters of developer regenerated at a rate of 250 ml per h with fresh developer.
  • the sheet materials were conveyed by rollers at a daily throughput of 30 m 2 through the developer in a developing machine PAKO 24 S (trade name).
  • the speed values defined as log exposure values at optical density 1.00 above fog were expressed as percentual values with respect to the speed 100 given arbitrarily to the result obtained in Test 1.
  • the fog values are the optical density values in the non-exposed area.
  • Compound is compound 3 of Table 1.
  • Compound 11 is an equimolar mixture of alkylphenoxy(OH 2 -CH 2 -O)n-PO-(OH) 2 and [alkylphenoxy(CH 2 -CH2-0)n)]2-PO-OH, wherein the alkyl group is a n-hexadecyl group and n is 15.
  • Compound III is 1-phenyl-5-mercaptotetrazole.
  • test 2 the developer liquid was completely free of 1-phenyl-5-mercapto-tetrazole.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (15)

1. Procédé de développement d'un matériau photographique exposé d'émulsion à l'halogénure d'argent, ce procédé consistant à traiter le matériau avec un liquide alcalin aqueux en présence de (i) un agent développateur, (ii) un composé mercapto hétérocyclique comportant un groupe aliphatique contenant au moins 3 atomes de carbone et (iii) un agent tensio-actif, caractérisé en ce que cet agent tensio-actif est un agent tensio-actif d'ester phosphate alkylphénoxy-polyalkylène-oxy anionique, tandis que le composé mercapto est un composé mercapto hétérocyclique répondant aux formules générales tautomères (A) et (B) ci-après:
Figure imgb0017
dans lesquelles
Z représente les atomes nécessaires pour fermer un noyau hétérocyclique azoté pentagonal ou hexagonal comprenant un groupe d'hydrocarbure d'au moins 7 atomes de carbone en ligne droite.
2. Procédé selon la revendication 1, caractérisé en ce que le composé mercapto héterocyclique est un mercapto-tétrazole, un mercapto-triazole, un mercapto-thiadiazole, un mercapto-oxadiazole, un mercapto-benzimidazole, un mercapto-benzoxazole ou un mercapto-benzthiazole.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le composé mercapto hétérocyclique est un mercapto-tétrazole répondant à la formule générale suivante:
Figure imgb0018
dans laquelle
R représente un substituant comprenant une chaîne hydrocarbonée contenant au moins 7 atomes de carbone en ligne droite.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'agent tensio-actif anionique est un composé mono- ou di-ester d'acide alkylphénoxy(éthylène-oxy)n phosphorique sous forme d'un sel, n étant un nombre entier positif d'au moins 4, tandis que le groupe alkyle est un groupe alkyle en C8 à C20.
5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le composé (ii) est utilisé dans le liquide alcalin aqueux en une quantité de 10-4 à 10-3 mole par litre.
6. Procédé selon l'une quelconque des revendications précedentes, caractérisé en ce que le composé (iii) est utilisé dans le liquide alcalin aqueux en une quantité de 50 à 200 mg/1.
7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on effectue le traitement en présence d'un agent anti-voile.
8. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le matériau photographique exposé contient le composé (iii) dans une couche perméable à l'eau déjà avant l'exposition.
9. Liquide activateur ou révélateur alcalin aqueux destiné à être utilisé lors du développement d'un matériau photographique photo-exposé d'émulsion à l'halogénure d'argent contenant un composé mercapto hétérocyclique comprenant un groupe aliphatique contenant au moins 3 atomes de carbone, ainsi qu'un agent tensio-actif, caractérisé en ce que cet agent tensio-actif est un agent tensio-actif d'ester phosphate alkylphénoxy-polyalkylène-oxy anionique, tandis que le composé mercapto est un composé mercapto hétérocyclique répondant aux formules générales tautomères (A) et (B) ci-après:
Figure imgb0019
dans lequelles:
Z représente les atomes nécessaires pour fermer un noyau hétérocyclique azoté pentagonal ou hexagonal, tandis qu'il comprend un groupe d'hydrocarbure contenant au moins 7 atomes de carbone en ligne droite.
10. Liquide selon la revendication 9, caractérisé en ce que le composé mercapto hétérocyclique est un mercapto-tétrazole, un mercapto-triazole, un mercapto-thiadiazole, un mercapto-oxadiazole, un mercapto-benzimidazole, un mercapto-benzoxazole ou un mercapto-benzthiazole.
11. Liquide selon la revendication 9 ou 10, caractérisé en ce que le composé mercapto hétérocyclique est un mercapto-tétrazole répondant à la formule générale suivante:
Figure imgb0020
dans laquelle:
R représente un substituant comprenant und chaîne hydrocarbonée contenant au moins 7 atomes de carbone en ligne droite.
12. Liquide selon l'une quelconque des revendication 9 à 11, caractérisé en ce que l'agent tensio-actif anionique est un composé de mono- ou de di-ester d'acide alkylphénoxy(éthylène-oxy)r, phosphorique sous forme d'un sel, n étant un nombre entier positif égal à au moins 4, tandis que le groupe alkyle est un groupe alkyle en C8 à C20.
13. Liquide selon l'une quelconque des revendications 9 à 12, caractérisé en ce que le composé mercapto est présent en une quantité de 10-4 à 10-3 mole par litre.
14. Liquide selon l'une quelconque des revendications 9 à 13, caractérisé en ce que l'agent tensio-actif est présent en une quantité de 50 à 200 mg/litre.
15. Liquide selon l'une quelconque des revendications 9 à 14, caractérisé en ce qu'il contient un agent anti-voile.
EP19850201959 1985-11-26 1985-11-26 Méthode pour le développement d'un matériau photographique à base d'émulsions à l'halogénure d'argent exposé Expired EP0223883B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP19850201959 EP0223883B1 (fr) 1985-11-26 1985-11-26 Méthode pour le développement d'un matériau photographique à base d'émulsions à l'halogénure d'argent exposé
DE8585201959T DE3568377D1 (en) 1985-11-26 1985-11-26 Method for developing an exposed photographic silver halide emulsion material
JP61280531A JPH07119972B2 (ja) 1985-11-26 1986-11-25 露光写真ハロゲン化銀乳剤材料を現像する方法

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EP19850201959 EP0223883B1 (fr) 1985-11-26 1985-11-26 Méthode pour le développement d'un matériau photographique à base d'émulsions à l'halogénure d'argent exposé

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EP0223883B1 true EP0223883B1 (fr) 1989-02-22

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0690457B2 (ja) * 1988-02-04 1994-11-14 富士写真フイルム株式会社 写真現像処理方法
JP2704287B2 (ja) * 1989-03-24 1998-01-26 コニカ株式会社 ハロゲン化銀写真感光材料の画像形成方法
US5215873A (en) * 1989-11-21 1993-06-01 E. I. Du Pont De Nemours And Company Process for developing silver halide recording materials
EP0518627A1 (fr) * 1991-06-10 1992-12-16 International Paper Company Réduction de boues d'argent pendant le traitement photographiques
EP0620484B1 (fr) * 1993-04-13 1997-02-05 Agfa-Gevaert N.V. Films radiographiques industriels à l'halogénure d'argent
EP0620483A1 (fr) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Traitement de films radiographiques industriels à l'halogénure d'argent
EP0621506A1 (fr) * 1993-04-13 1994-10-26 Agfa-Gevaert N.V. Traitement de films radiographiques industriels à l'halogénure d'argent
EP0620482A1 (fr) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Méthode de traitements de films radiographiques à l'halogénure d'argent pré-durcis
US5506092A (en) * 1993-12-06 1996-04-09 Konica Corporation Method of processing black and white silver halide photographic compositions with a developer containing an anti sludgant
US5457011A (en) * 1993-12-27 1995-10-10 Eastman Kodak Company Photographic developing composition containing a sludge inhibiting agent and use thereof in the high contrast development of nucleated photographic elements

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1314087A (fr) * 1960-12-29 1963-01-04 Gevaert Photo Prod Nv Procédé pour améliorer les propriétés physiques d'un matériel photographique
DE1801330A1 (de) * 1968-10-04 1970-04-23 Eastman Kodak Co Verfahren zur Herstellung von schwarz getoenten,positiven Silberbildern nach dem Silbersalzdiffusionsuebertragungsverfahren
JPS495334A (fr) * 1972-04-28 1974-01-18
JPS56142529A (en) * 1980-04-07 1981-11-06 Fuji Photo Film Co Ltd Developing method for silver halide photographic sensitive material
JPS5711341A (en) * 1980-06-25 1982-01-21 Fuji Photo Film Co Ltd Photographic sensitive material
JPS5822734A (ja) * 1981-08-04 1983-02-10 Nissan Motor Co Ltd 上下調節式パ−セルシエルフ
JPS58171036A (ja) * 1982-03-25 1983-10-07 Konishiroku Photo Ind Co Ltd 写真画像の形成方法
JPS5968732A (ja) * 1982-10-13 1984-04-18 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
IT1175017B (it) * 1983-09-20 1987-07-01 Minnesota Mining & Mfg Composizioni di sviluppo per materiali fotografici agli alogenuri d'argento

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JPH07119972B2 (ja) 1995-12-20
JPS62131252A (ja) 1987-06-13
DE3568377D1 (en) 1989-03-30
EP0223883A1 (fr) 1987-06-03

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