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
  • G03C5/30—Developers
  • G03C5/3028—Heterocyclic compounds
  • G03C5/3035—Heterocyclic compounds containing a diazole ring

Definitions

• This invention relates in general to photography and in particular to the development of X-ray films. More specifically, this invention relates to an improved aqueous alkaline photographic developing solution that is especially adapted for use in the development of fore-hardened X-ray films.
• developing solutions for use with X-ray film have typically been formulated using hydroquinone as the primary developing agent, 1-phenyl-3-pyrazolidinone as a super-additive auxiliary developing agent and glutaraldehyde as a hardening agent.
• These developing solutions have been packaged as three-part formulations.
• the need for the added cost and complexity of three-part packaging has been dictated by the fact that glutaraldehyde tends to react with 1-phenyl-3-pyrazolidinone, that 1-phenyl-­3-pyrazolidinone tends to oxidize in alkaline solution, and that glutaraldehyde tends to polymerize in alkaline solution.
• the hydroquinone has been packaged in a first part which is alkaline
• the 1-phenyl-3-pyrazolidinone has been packaged in a second part which is acidic
• the glutaraldehyde has been packaged in a third part which is acidic.
• the three parts Prior to use, the three parts are blended together and diluted with water to give the appropriate concentration and alkaline pH for use as working developing solution.
• Representative of the prior art relating to developing solutions for use with X-ray films are U. S. Patents 3,545,971, 4,046,571, 4,672,025 and 4,810,622, all of which describe developing solutions that contain aldehydic hardening agents, such as glutaraldehyde, and are packaged as three-part formulations.
• Aldehydic hardening agents are not needed in developing solutions intended for use in processing X-ray films which have been adequately fore-hardened, such as those described in U. S. Patent 4,414,304.
• the fore-hardened tabular grain emulsions of Patent '304 offer the advantage of exhibiting high levels of covering power that are relatively insensitive to increasing levels of fore-hardening.
• the radiographic elements of Patent '304 ingest less water during processing and therefore lend themselves to accelerated processing, typically to total processing times of 45 seconds or less.
• this invention is directed to an aqueous alkaline photographic developing solution especially adapted for use in the development of fore-hardened X-ray films, said developing solution having a pH in the range of 9 to 12, being substantially free of both aldehydic hardening agents and silver halide solvents and comprising a dihydroxybenzene developing agent, an auxiliary super-additive developing agent, an alkaline agent, an organic anti-foggant and a preservative; characterized in that said super-additive auxiliary developing agent is present in a concentration of at least 3.5 grams per liter of said developing solution and is a 4,4-disubstituted-1-aryl-3-pyrazolidinone of the formula: wherein R1 and R2 are the same or different and each is alkyl of 1 to 6 carbon atoms or hydroxyalkyl of 1 to 6 carbon atoms, and R3 is hydrogen, halogen, alkyl of 1 to 6 carbon atoms or alkoxy of 1 to 6 carbon atoms
• the developing solution of this invention is free, or at least substantially free, of aldehydic hardening agents such as glutaraldehyde. Since the developing solution is intended for use with X-ray films that have been adequately fore-hardened, the incorporation of hardening agents in the developing solution is unnecessary.
• the developing solution of this invention is free, or at least substantially free, of silver halide solvents, such as thiosulfates or thiocyanates, as these solvents are detrimental to its performance in development of fore-hardened X-ray films and would provide unacceptable sensitometry.
• silver halide solvents such as thiosulfates or thiocyanates
• the dihydroxybenzene developing agents employed in the aqueous alkaline developing solutions of this invention are well known and widely used in photographic processing.
• the preferred developing agent of this class is hydroquinone.
• Other useful dihydroxybenzene developing agents include: chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 1,4-dihydroxy-2-acetophenone-2,5-dimethylhydro­quinone, 2,5-diethylhydroquinone, 2,5-di-p-phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, 2,5-diacetaminohydroquinone, and the like.
• the developing solution must include a 4,4-disubstituted-1-aryl-3-pyrazolidinone, of the structure indicated hereinabove, which functions as an auxiliary super-additive developing agent.
• 4,4-disubstituted-1-aryl-3-pyrazoli­dinone developing agents include: 4,4-dimethyl-1-phenyl-3-pyrazolidinone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone (HMMP), 4,4-di-(hydroxymethyl)-1-phenyl-3-pyrazolidinone, 4,4-diethyl-1-phenyl-3-pyrazolidinone, 4-methyl-4-ethyl-1-phenyl-3-pyrazolidinone, and the like.
• Suitable alkaline agents which can be included in the developing solution to maintain the desired alkaline pH include hydroxides such as sodium hydroxide or potassium hydroxide, bicarbonates such as sodium bicarbonate or potassium bicarbonate, and borates such as sodium tetraborate.
• an effective amount of an organic antifoggant is included in the developing solution of this invention. Particularly advantageous results are achieved with the use of benzotriazole antifoggants.
• a further preferred class of organic antifoggants are the mercapto azole and mercapto azine antifoggants.
• Inorganic antifoggants or restrainers, such as alkali metal bromides, can be utilized in conjunction with the use of an organic antifoggant, if desired.
• Preferred mercapto azole or mercapto azine antifoggants are those represented by the formula: wherein Z represents the atoms necessary to complete a 5 or 6 member heterocyclic ring, such as pyrimidine, triazine, tetrazole, triazole, imidazole, diazole, oxadiazole or thiadiazole ring; and SX represents a mercapto function, n being a whole number, typically a number from 1 to about 3, any free bonds being satisfied by hydrogen atoms.
• X is a cation which includes hydrogen, an alkali metal, e.g., sodium or potassium, ammonium or an organic amine residue of such amines as triethyl amine, triethanolamine, morpholine and the like.
• Mercapto tetrazole antifoggants are especially suitable in the practice of this invention and include those of the formula: wherein R is an aliphatic or aromatic radical containing up to about 30 carbon atoms and SX is a mercapto function.
• benzotriazole antifoggants for use in the developing solutions of this invention are benzotriazole, halo-substituted benzotriazoles such as 4-chlorobenzotriazole; 4-bromobenzotriazole and 5-chlorobenzotriazole, and alkyl-substituted benzotriazoles such as 5-methyl­benzotriazole.
• mercapto azole antifoggants include: mercapto-substituted pyrimidines such as thiobar­bituric acid and thiouracil, mercapto-substituted oxadiazoles or thiadiazoles such as 5-phenyl-2-mercapto-1,3,4-oxadiazole and 5-o-tolyl-2-mercapto-1,3 ,4-thiadiazole, mercapto triazines such as 2,4,6-trimercapto-1,3,5-­triazine, mercapto imidazoles such as 2-mercapto-5-phenyl-­imidazole, condensed imidazoles such as 2-mercaptobenz­imidazole, triazoles such as 3,4-diphenyl-5-mercapto-1,2,4-­triazole and 3-mercapto-5-methyl-1,2,4-triazole, mercapto tetrazoles such as 1-phenyl-5
• the aqueous alkaline photographic developing solutions of this invention preferably contain a sulfite preservative at a level sufficient to protect the developing agents against aerial oxidation and thereby promote good stability characteristics.
• Useful sulfite preservatives include sulfites, bisulfites, metabisulfites, and carbonyl bisulfite adducts.
• Typical examples of sulfite preservatives include: sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde bisulfite, and the like.
• preservatives such as hydroxylamine and ascorbic acid can be used instead of or in combination with the sulfites.
• the aqueous alkaline photographic developing solution of this invention can optionally contain other ingredients including sequestering agents, surfactants, and organic solvents such as diethylene glycol.
• aminopolycarboxylic acid sequestering agents are particularly useful in the developing solutions of this invention.
• Typical examples of the aminopolycarboxylic acid sequestering agents include: nitrilotriacetic acid, (NTA), ethylenediaminetetraacetic acid, (EDTA), 1,3-propylenediaminetetraacetic acid (PDTA), 1-3-diamino-2-propanol-N,N,N′,N′-tetraacetic acid (DPTA), diethylenetriaminepentaacetic acid (DTPA), N,N′-bis(2-hydroxybenzyl) ethylenediamine-N,N′-­diacetic acid (HBED), hydroxyethylenediaminetriacetic acid, cyclohexanediaminotetraacetic acid, aminomalonic acid, and the like.
• NTA nitrilotriacetic acid
• EDTA ethylenediaminetetraacetic acid
• PDTA 1,3-propy
• the aqueous alkaline developing solutions of this invention can vary widely in regard to the concentration of the various ingredients included therein.
• the dihydroxybenzene developing agent e.g., hydroquinone
• the 4,4-disubstituted-1-aryl-3-pyrazolidinone e.g., 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone
• the alkaline agent e.g., potassium hydroxyde
• the organic antifoggant e.g., 5-méthyl-benzotriazole
• the preservative e.g., potassium sulfite
• the developing process is typically carried out at a temperature of about 25°C to about 50°C.
• very short developing times such as times of 10 seconds, or less, are feasible, with total processing times of 45 seconds or less being contemplated.
• fore-hardened radiographic elements when processed in the following 45 second cycle using the developer of this invention can produce sensitometric character­istics matching those obtained with conventional radiographic products processed in a 90 second cycle using an aldehydic developer: development 10.2 sec. 35°C fixing 8.7 sec. 35°C washing 7.2 sec. 35°C drying 17.0 sec. 65°C Time otherwise unaccounted for is used for film transport.
• a particularly preferred aqueous alkaline photographic developing solution within the scope of this invention is a solution consisting essentially of 25 to 50 grams per liter of hydroquinone, 4 to 8 grams per liter of 4-hydroxymethyl-4-methyl-1-phenyl-3-­pyrazolidinone, 5 to 10 grams per liter of sodium bicarbonate, 20 to 40 grams per liter of potassium hydroxide, 0.1 to 0.3 grams per liter of 5-methyl-­benzotriazole, 50 to 80 grams per liter of potassium sulfite, 5 to 10 grams per liter of sodium metabisulfite, 1 to 4 grams per liter of sodium bromide, 10 to 30 grams per liter of diethylene glycol and 2 to 4 grams per liter of diethylenetriaminepenta­acetic acid.
• Aqueous alkaline photographic developing solutions were prepared in accordance with the following formulations: Table I Amount (grams) Ingredient EX 1 EX 2 Ex 3 Ex 4 Sodium metabisulfite 8.0 8.85 8.85 8.85 Potassium hydroxide (45% solution) 60.0 50.0 57.8 60.0 Diethylenetriamine-pentaacetic acid (40% solution) 7.1 7.1 7.1 7.1 Sodium bromide 2.25 2.25 2.25 2.25 Sodium bicarbonate 7.5 7.5 7.5 Potassium sulfite (45% solution) 119.3 159.0 159.0 159.0 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone 3.5 5.0 4.51 3.67 5-Methylbenzotriazole 0.12 0.12 0.151 0.119 Diethylene glycol 20.0 20.0 20.0 20.0 Hydroquinone 39.0 32.0 34.2 51.3 Water to one liter pH at 25°C 10.7 10.5 10.83 10.71
• the above-described developing solutions were each employed at a temperature of 35°C to develop a fore-hardened X-ray film as described in U. S. patent 4,414,304. Development was completed in 10.2 seconds in each of Examples 1 and 2, in 9.2 seconds in Example 3 and in 7.8 seconds in Example 4. The total processing cycle time was 45 seconds for Examples 1 and 2, 40 seconds for Example 3, and 35 seconds for example 4. Measurements were made with respect to gross fog, film speed at a density of 1.0 above gross fog (1.0CR), mid scale contrast (MSC), lower scale contrast (LSC), upper scale contrast (USC), and upper density point (UDP) and were found, in each case, to be acceptably similar to those obtained in the standard KODAK RP X-OMATTM process. Each of the developing solutions was capable of being formulated and packaged as a single-part composition which exhibited acceptable shelf life and stability.
• a radiographic product intended to be processed in an aldehydic developer such as a Kodak RP X-OmatTM 90 second process.
• the developer exhibited the following composition: Hydroquinone 22 g 1-Phenyl-3-pyrazolidone 1.35 g KOH 19.32 g NaHCO3 5.81 g K2SO3 75 g NaBr 3.5 g 5-Methylbenzotriazole 0.06 g Glutaraldehyde 4.44 g Water to 1 liter at pH 10.1
• Example 5 developer had the following composition: Hydroquinone 32 g HMMP 6 g KOH 24.4 g NaHCO3 7.5 g K2SO3 75 NaBr 2.25 g 5-Methylbenzotriazole 0.12 g Water to 1 liter at pH 10.35
• a radiographic element identical to that employed in Example 2 was processed in the Example 5 developer using the following 45 second process cycle: development 10.2 sec. 35°C fixing 8.7 sec. 35°C washing 7.2 sec. 35°C drying 17.0 sec. 65°C Time not otherwise accounted for was consumed in film transport.

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• 1990
  • 1990-10-01 CA CA 2026606 patent/CA2026606A1/en not_active Abandoned
  • 1990-10-31 EP EP19900420470 patent/EP0428455A3/de not_active Withdrawn
  • 1990-11-05 JP JP29734190A patent/JPH03161744A/ja active Pending

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