US3240603A - Photographic developer solution containing non-sludging silver halide solvent - Google Patents

Photographic developer solution containing non-sludging silver halide solvent Download PDF

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Publication number
US3240603A
US3240603A US141296A US14129661A US3240603A US 3240603 A US3240603 A US 3240603A US 141296 A US141296 A US 141296A US 14129661 A US14129661 A US 14129661A US 3240603 A US3240603 A US 3240603A
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grams
silver halide
fixing
mercapto
hydroxy
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US141296A
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English (en)
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Schuler Horst
Grabhofer Herbert
Ulrich Hans
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38Fixing; Developing-fixing; Hardening-fixing
    • G03C5/383Developing-fixing, i.e. mono-baths

Definitions

  • Photographic processing solutions in which a silver halide solvent is added to a developer solution have been known for more than 60 years.
  • These combined developing and fixing solutions also known as a monobath, are generally prepared by combining a developer solution which contains all the conventional developer ingredients with water-soluble thiosulfate salts such as sodium thiosulfate or ammonium thiosulfate which acts as a silver halide solvent.
  • Other silver halide solvents which have been proposed for a monobath solution, include potassium thiocyanate and potassium cyanide, but the latter cannot be used in practice because it is a lethal poison.
  • the two processes of development and fixing proceed separately and simultaneously.
  • the sensitometric properties of the final results can be influenced within certain limits depending on the kinetic characteristics of the two processes.
  • N C-R1 I-IS(3 D-X N-(i-OH wherein R represents hydrogen, alkyl such as methyl, ethyl, propyl, isobutyl, butyl and the like; aryl, such as phenyl, tolyl and the like; aralkyl, such as benzyl, phen- 3,240,603 Patented Mar.
  • carboxyalkyl such as carboxymethyl, carboxyethyl, carboxypropyl
  • X represents, in addition to hydrogen, the grouping CH2-N wherein R and R are lower alkyl groups having the value given above for R and the group wherein Y represents the atoms necessary to complete a heterocy-clic nucleus, such as a piperidine and morpholine nucleus.
  • the combined fixing and developing solution prepared with the above 2-rnercapto-o-hydroxypyrimidine derivatives are superior to the previously known monobath solutions because they remain free from silver sludge even after extended use and development of large quantities of film. Thus, the keeping qualities of the combined fixing developing solutions are noticeably improved on use.
  • the combined fixing and developing solution of this invention otter the advantage of dissolving all of the undeveloped silver halide left in the emulsion layer. For this reason, our new monobaths are eminently suitable for the processing of photographic transparencies.
  • the fixing developers of our invention can be used for the processing of films and paper.
  • the processing time required varies somewhat with the type of photographic material and with the extent of agitation but is generally within a time limit of from two to seven minutes.
  • any of the known photographic developing agents such as hydroquinone, paramethylaminophenol sulfate (Methol), 1-phenyl-3-pyrazolidone (Phenidone), 1- (p-methylaminophenyl) -3 -amino-A-2-pyrazoline, 4-aminopyrazolone and the like.
  • the combined developer fixer solutions may also contain the usual developer additives including sequestering agents, such as ethylenediamine, tetracetic acid and its alkali metal salts; an alkali, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate; an antioxidant, such as an alkali metal sulfite or bisulfite; developer accelerators, such as cetyl pyridinium bromide or thallium nitrate; antifoggants, such as potassium bromide, sodium bromide, nitrobenzimidazole; and, substances which influence the image tone and act also as restrainers such as mercaptobenzimidazole and mercaptobenzothiazole, benzotriazole and phenylmercaptotetrazole.
  • sequestering agents such as ethylenediamine, tetracetic acid and its alkali metal salts
  • an alkali such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate
  • a thickening agent such as sodium carboxymethylcellulose, tragacanth, the copolymer of an alkyl vinyl ether and a maleic acid derivative or similar materials makes it possible to obtain fixing developers having a paste-like consistency which can be used for processing paper and film in certain developing equipment which requires the use of highly viscous processing solutions.
  • PREPARATION II Z-mercapto-6-hydroxy-4-carboxymethylpyrimidine us CH 70 grams of thiourea and 202 grams of the diethyl ester of acetone dicarboxylic acid were added to a solution of 23 grams of sodium in 1 liter of absolute alcohol and the mixture heated for three hours under reflux. The alcohol was evaporated, the residue dissolved in water and weakly acidified with hydrochloric acid. An oil separated which solidified on stirring with a glass rod. The purification was carried out by recrystallizing the product from a mixture of one part of water and two parts of alcohol; M.P. 158 C.
  • PREPARATION IV 2 mercapto 6 hydroxy 5 (dimethylaminometh ylene)-pyrimidine 12.8 grams of thouracil, 33.8 grams of a 40% aqueous solution of dimethylamine, grams of a formaldehyde solution, 1 milliliter of glacial acetic acid and 250 milliliters of alcohol were heated for four hours under reflux. The alcohol was distilled off and the residue recrystallized from aqueous alcohol; M.P.
  • PREPARATION VII 2 mercapto-4-rnethyl-6-hydroxy-5-(N-morpholylmethylene -pyrimidine 26.1 grams of morpholine, 20.0 grams of a 30% formaldehyde solution, 1 mol of glacial acetic acid and 12.8 grams of thiouracil and 250 milliliters of alcohol were heated under reflux for five hours. The alcohol was then distilled off and the residue recrystallized from aqeous ethanol; M.P. 223 C.
  • PREPARATION VIII 2 mercapto-6-hydroxy-4-phenylpyrimidine (4-phenyl- 2-thiouracil) 11s on 11.5 grams of sodium dissolved in 500 milliliters of absolute alcohol were mixed with 96 grams of ethyl" benzoylacetate and 39 grams of thiourea. The mixture: was heated under reflux for five hours. The reaction: product which had separated was dissolved in hot water, treated with charcoal and precipitated with glacial acetic acid. The compound recrystallized from glacial acetic acid; M.P. 270 to 273 C.
  • Example I An exposed panchromatic black and white 35 mm. film having a sensitivity of 13 DIN, commercially available under the name of Agfa Isopan I FF film, was processed in a monobath having the following composition:
  • Example II A blue-sensitive black and white film used for photomechanical reproduction and commercially available as Agfa Phototechnisch B was processed in a monobath of the following composition:
  • Example 111 A graphic art film of the type used in Example II was processed in a combined fixing and developing solution having the following composition:
  • Example IV A graphic art type black and white film as described in Example II was processed in a monobath having the following composition:
  • Example V A silver chloride contact printing paper was processed in a monobath having the following composition:
  • Example VII A film as used in Example I was developed in a monobath of the following composition:
  • the developed, washed and .dried film had a gamma of 0.6 and a fog of 0.14.
  • Example IX A film as used in Example I was developed in a fixing developer of the following composition:
  • Example X An orthochromatic microfilm (Agfa Agepe) was processed in a fixing developer having the following composition:
  • Example XI A film as used in Example I was developed in a fixing developer of the following composition:
  • Example XII A film as used in Example I was developed in a fixing developer of the following composition:
  • This paste was applied to the exposed paper and removed after three minutes developing time.
  • a combined photographic developing and fixing bath composition comprising an alkaline photographic silver halide developer solution containing a silver halide solvent of the following general formula:
  • N CR1 ri -('1 I-X IQ-(i-OH)
  • R is a member of the group consisting of a hydrogen atom, lower alkyl, phenyl, tolyl, benzyl, phenethyl and lower carboxy-alkyl groups
  • X is a member of the group consisting of hydrogen, the grouping wherein R and R each represents a lower alkyl group, and the grouping wherein Y represents the atoms necessary to complete a mononuclear ring.
  • a combined photographic developing and fixing composition according to claim 1 which contains in addition to said developer and fixing agent a thickening agent so as to provide the combined fixing and developing composition with a paste-like consistency.
  • a combined developing and fixing bath solution according to claim 1 wherein said silver halide solvent is 2-mercapto-6 hydroxy 5 (dimethylaminomethylene)- 4-methylpyrimidine.
  • a combined developing and fixing bath solution according to claim 1 wherein said silver halide solvent is 2 mercapto 6 hydroxy 5 (N piperidylrnethy1ene)- pyrimidine.
  • a combined developing and fixing bath solution according to claim 1 wherein said silver halide solvent is Z-mercapto 6 hydroxy 5 (N morpholylmethylene)- pyrimidine.
  • a combined developing and fixing bath solution having the following composition:
  • a combined developing and fixing bath solution having the following composition:
  • a combined developing and fixing bath solution having the following composition:
  • a combined developing and fixing bath solution having the following composition:
  • a combined developing and fixing bath solution having the following composition:

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US141296A 1960-09-29 1961-09-28 Photographic developer solution containing non-sludging silver halide solvent Expired - Lifetime US3240603A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA35690A DE1163142B (de) 1960-09-29 1960-09-29 Photographischer Fixierentwickler

Publications (1)

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US3240603A true US3240603A (en) 1966-03-15

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US (1) US3240603A (fr)
BE (1) BE608301A (fr)
DE (1) DE1163142B (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3400836A (en) * 1966-12-28 1968-09-10 Budd Co Retracting clamp
US3819378A (en) * 1972-03-10 1974-06-25 Gen Film Dev Corp Fine grain high speed photographic processing monobath composition
US3857710A (en) * 1972-12-22 1974-12-31 Gen Film Dev Corp High contrast, high capacity monobath processing method and composition for monochrome film
EP0500045A1 (fr) * 1991-02-19 1992-08-26 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique à l'halogénure d'argent et composition photographique ayant une capacité de fixage
US5356761A (en) * 1991-04-02 1994-10-18 Fuji Photo Film Co., Ltd. Development of silver halide photosensitive material and developer
US5510231A (en) * 1993-04-27 1996-04-23 Konica Corporation Solid developing composition for silver halide photographic light-sensitive material and processing method using the same
US6037115A (en) * 1996-05-22 2000-03-14 Eastman Kodak Company Photothermographic and thermographic films containing low levels of formate to prevent fog
US6040130A (en) * 1997-02-10 2000-03-21 Eastman Kodak Company Photothermographic and thermographic films containing low levels of unsaturated fatty acid to prevent fog
CN109240037A (zh) * 2018-11-07 2019-01-18 天津市康华健晔医用材料有限公司 一种环保显定影冲洗液

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2525532A (en) * 1946-10-18 1950-10-10 Eastman Kodak Co Simultaneously developing and fixing photographic images

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1077059B (de) * 1956-08-28 1960-03-03 Leonar Werke Ag Verfahren zur Schnellentwicklung photographischer Schichten

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2525532A (en) * 1946-10-18 1950-10-10 Eastman Kodak Co Simultaneously developing and fixing photographic images

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3400836A (en) * 1966-12-28 1968-09-10 Budd Co Retracting clamp
US3819378A (en) * 1972-03-10 1974-06-25 Gen Film Dev Corp Fine grain high speed photographic processing monobath composition
US3857710A (en) * 1972-12-22 1974-12-31 Gen Film Dev Corp High contrast, high capacity monobath processing method and composition for monochrome film
EP0500045A1 (fr) * 1991-02-19 1992-08-26 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique à l'halogénure d'argent et composition photographique ayant une capacité de fixage
US5356761A (en) * 1991-04-02 1994-10-18 Fuji Photo Film Co., Ltd. Development of silver halide photosensitive material and developer
US5510231A (en) * 1993-04-27 1996-04-23 Konica Corporation Solid developing composition for silver halide photographic light-sensitive material and processing method using the same
US6037115A (en) * 1996-05-22 2000-03-14 Eastman Kodak Company Photothermographic and thermographic films containing low levels of formate to prevent fog
US6040130A (en) * 1997-02-10 2000-03-21 Eastman Kodak Company Photothermographic and thermographic films containing low levels of unsaturated fatty acid to prevent fog
CN109240037A (zh) * 2018-11-07 2019-01-18 天津市康华健晔医用材料有限公司 一种环保显定影冲洗液

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Publication number Publication date
DE1163142B (de) 1964-02-13
BE608301A (fr) 1962-01-14

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