CA1181624A - Stable photographic developer and replenisher therefor containing 1-phenyl-3-pyrazolidone and hydroquinone - Google Patents
Stable photographic developer and replenisher therefor containing 1-phenyl-3-pyrazolidone and hydroquinoneInfo
- Publication number
- CA1181624A CA1181624A CA000407806A CA407806A CA1181624A CA 1181624 A CA1181624 A CA 1181624A CA 000407806 A CA000407806 A CA 000407806A CA 407806 A CA407806 A CA 407806A CA 1181624 A CA1181624 A CA 1181624A
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- Prior art keywords
- developer
- photographic
- replenisher
- film
- solution
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Classifications
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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
- 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
-
- 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
- G03C5/31—Regeneration; Replenishers
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An aqueous photographic silver halide developer/replenisher solution particularly useful in low throughput machine processing of X-ray silver halide elements.
An aqueous photographic silver halide developer/replenisher solution particularly useful in low throughput machine processing of X-ray silver halide elements.
Description
TITLE
STABLE PHOTOGRAPHIC DEVELOPER
AND REPLENISHER THEREFOR
'le ~:
Thi~ invention is in the field of photographic silver halide developer solutions and replenishers therefor, and is specifically dir~c~ed to developer~replenisher solutions useful in low through-put machine processing (developing) of 10 photographic film.
8ao k~ound Ar t:
The use of so-called "automatic processors"
is conventional for developing imagewise exposed 5ilve~r halide elements such as ~-ray f ilms . The 15 exposed ilms are fed into the processor from a sa~eli~ht area~ i.e. one in whi~h the level of light is reduced below that which exposes th~ film further~
and is transported through various chambers containing the developer, the fixer and the water 29 washes. At th end of the processor, the film. is dried and exits into normal light as a finished ~product ready for use. This is illustrated in U.SO
Pat~nt 3,545,971 "Rapid Proce~sing of Photographic X-ray Film" (1966). This system is rapid and 25 convenien~ and large numbers of films can be routinely handled in this manner over long periods of time without dele~erious effec~s to the finished image. Of cou~set the processing solutions become exhausted by the passage of the exposed silver halide film and replenishmen~ mus~ be made to account for ingredient loss. Addi~ionally, the processing flui~s, especially the developer solution, are degraded aerobic~lly by contact with air and anerobically when simply left for long periods of P~-1810 35 inaction.
'~
When large amounts of ~ilm are being processed (high throughpu'c), exhaustion of ~he developer is due almost entirely to devalopment s~f the s ilver hal ide image . The developmen ~ reaction as 5 shown in Mason's "Pho~ographic Processing Ch~mis~xy"
Focal Press (1966~ page 74, is~
2AgBr ~ H2Q + Na2S03 ~ 7Ag ~ ~Br ~ NaBr + ElQS03Na Thus, some materials, i.e., hydroquinone and sulfite are lost while bromide, acld, and hydroquinone 19 mono~ulfonate are formed~ Also, no~ shown by this reaction, antioggant may be los~. Curren~ devPloper replenishers are formulated based on this reaction as follows: The replenisher is made higher in pH ~han developer and contains no bromide t SO as to offset the acid and bromide released by the development reaction. ~he other ingredients are se~ at concentrations whirh allow for ~he ~xpec~ed losses, the hydroquinone being offset by ~he antifoggants, without substantially affecting the sensi~ometry. In 20 this situation a replenishment rate can be co~veniently calculated ba~ed on the approximate area of film fed into the processor.
The other situation presen~s a more difficul t problem because when only small amounts of ~ilm are processed (low throughput), the developer deteriorates primarily from air oxidation and thermal reactions r and not from development reaction; Mason's ~Photographic Processing Chemistry~ supra at page 73:
2Q a~ 3 2 ~ HQS03Na ~ NaO~ ~ Na2S04.
That is, hydroquinone and sulfite are lost bu~ not bromide. Also, p~ increases, not decreases as in the development reaction. Also, since film passage activates the replenishmen~, low throughput decr~ases replenishment.
Current practice is to compensate for low throughput by increasing replenishment rate significan~ly e.gO~ as much as two-fold. This, however, can actually accelerate the problems caused by low throughput processing and cause sensitometric instability~ ~ does so because the replenisher, which is being added, in ~xcess, has higher p~I than the developer and no bromide. The effec~ of this is to (1) maintain the increasiny p~ of the developer 10 caused by oxid2tion, and (2) dilute the bromide content to levels so low as ~o cause sensitometric instability, reflected mainly in fog ~nd speed~ The presen~ inven~ion provides a replenisher formula~ion whieh is aimed at compensating for developer changes caused by nonuse, and not by the development reaction. Thus, ~he replenisher is characterized by a p~ lower ~han ~ha~ of ~he developer, and it contains the maximum amoun~ of bromide consistent with acceptable sensitometr.y. Now when replenishment occurs, pH will remain constant or slightly ~ecr~ase, the bromide will remain essentially constan , and the o~her changes will compensate as in state of the art formulations. Thus ~ by maintaining the developer composition more constant, the developer can maintain a useful lifetime e~uivalent to the high throughput processors.
I~ is accordingly an object of thls invention to provide an improved developer/-replenisher system for developing exposed silver 30 halide photographic filmO A further object is to provide a developer/replenisher sys-tem par~icularly useful for machine processing of X~ray film when low throughput s~f film is practised.
Summar~ of the Invention:
These and other objects are achieved in this invention by providing an aqueous processing solution useful as a photographic developer bath for automatic processing of silver halide photographic film, parti-cularly X-ray film, and as a replenisher therefor, consisting essentially of, per liter:
l-phenyl-3-pyrazolidone photographic developing 10 agent, or a derivative thereof 0.8 to 2.5 g Hydroquinone developing agent or a derivative thereof15 to 35 g Bromide ion 1 to 7 g Organic antifoggant and film speed restrainer 0.01 to 2.66 m mole Alkaline material and buffer to provide a pH of 10.0 + 0.3;
with the proviso that the replenisher solution will not only contain bromide ion but also will have a lower pH than tha-t of the developer solution.
Developers and replenishers made according to this invention can be used in processing machines for low throughput of X-ray film, for example, and will exhibit excellent stability over long periods of both use and nonuse. Hence, a further embodiment of the invention is a process for the automatic processing of exposed photographic silver halide X-ray film wherein the imagewise exposed X-ray film is developed in a photographic developer bath comprising a photographic developer, bromide ion, an alkaline material and buffer system to maintain the pH of the developer bath at a desired value, an organic antifoggant and film speed restrainer, and water; the developed X-ray film is fixed, washed and dried; and the developer bath is replenished by a ~J
replenisher solu~ion ts~ maintain constant the photographic properties o~ the developer bath during pro::essing of a large quanti~y o: exposed X~ray film~
characterized in that ~he processing solu~ion 5 described above serves as bo~ch ~he deveïoper ba~h and the replenisher ss:~lution; with ~he proviso that the la~ter have a pH lower 'chan ~hat of the developer.
Detailed Di~closure of ~he Xn~7ention:
The processing ~olu~ion of this inventior 10 can be used for both the develQper and the replenisher therefor~ In the lat~er embodiment, wherein the replenisher solution has a lower pH than ~hat of the developer, it is only necessary to add a small amount of acid, acetic acid, for example, to 15 ad~u~t the pH. However, for a commercial pu~-up~ a small amount of base (alkaline ma~erial~ is added to ~he develop~r to raise the pH of the developer rather ~han adding acid to the replenisher ~o lower its pH.
This will be illustra~ed in Example 1, wherein a 20 ~mall amount of base is added through the starter sol~ltion ~Part D). The replerlisher is added to the developer bath as needed, based on ~ime and/or the amount o film proc:essed, thus compensa~ing for both forms of developer exhausltion. It is surprising ~hat 25 this particular f ormulation can be used so successfull5~ for low throughput in automatic processors ~ince the di~erences b~tween it and the prior art are so slight. E~owever, as will be seen in the Examples, the difference in performance between the formulation of this invention and the prior art is very la~ge.
As the photographic developing agents in the processing solution, a combina~ion of l-phenyl-3-pyrazolidone (sold under the Ilford trademark Phenidone) or a derivative thereof such as 4-mel:hyl or 4 / 4-dimethyl phenidone, and hydroquinone or a derivative thereof such as chlorohydroquinone or bromohydroquir~ne is used. This combin~tion is parti~ularly suited fs~r automatic p~ocessing of X-ray 5 ilms, These ordinarily comprise a gelatins~-Ag33r, AgBrI, or AgClE~rI emulsion on a film support such as polyethylene ~erephthalate.
~ ny alka].ine material may be used to provide the required pH, such as sodium or potassillm 10 hydroa~ide~ sodium or potassium carbonatel etc. The buffer sysi:em may be any converlient systemy e.g., the borate and carbonate bu~fers conventionally used in X~ray developer baths are both suitable.
Th~ organic antifog~ant may be any organic antifoggant and film speed restrainer. Such organic antifoggants are commonly employed in X-ray developer baths and include compounds of the benzimidazole, benzotriazole~ benzothiazole, indazole~ ~etrazole, and thiazole groupJ as well as anthraquinone sulfonic acid salts. Two or more organic antifoggant~ may be used9 ~t is preferred to use a mixture of ~wo antifoggan~s such as 5 nitroindazole and benzo~riazole.
A range of bromide ion can be used successfully in this inven~ion and provides excellent stability. 1 to 10 g/liter of KBr, for example, will provide sufficient bromide ion. NaBr may also be employed. Optimum amounts depend on replenishment rate and specific formula.
These essential ingredients, when dissolved in water at the concentrations se~ f orth above, enable the photographic solution of ~he invention to function as a developer bath and a shelf-stable replenisher .
.
Other materials may be included in the processing solution, such as gelatin hardening agen~s, aerial oxidation res~rainers, sequestering agents, surfactants, dyes, etc., as well known in the art. See, e.g., U~S~ Patent 3,545,971 and ~Photographic Processiny Chemistry", supra, page 149 et seq~
Conventionally, all of ~he inyredients of the developer are prepared in con entrated form in water. Separate portions of the concentrates are furnished users so that interaction between ingredients is lessened while in ~hiq concentra~ed state. Then, the user makes up the developer solution by measuring various amounts from each part 15 and diluting with water to achieve the desired ~olu~:ion. The pH is then adjusted, e.g~, to 10~0 + 0. 3, and the soluticn charged ~o the.
p~ocessing tank~ e.gI, of the type described in U.S.
Patent No. 3,545,971, such as an "X Omat Processor"~
in the amount reguired by the system. Developm nt time is determined empirically or by the processor.
Replenishment will be carried out al: a rate per unit area of exposed ilm to provide processing of a large quantity of exposed film without change in ~5 sensi~ometric properties of the fi.~m, ~nd will be determined empirically, as is known. As a guide, when using an X~Omat Processor to process X-ray film, a suitable replenishment rate will be about 55 ml per 240 square inches o exposed ~ilm for development to normal radiographic density, usiny the processin~
solution o the invention.
Some processors have a standby replenishment mode. This works as follows: if no film is passed in a given time, the proc:essor goes into a standby mode which deactivates the drive train and dryer and reduces water supply. After a given time, it comes back on for several minu~es and then shuts off ayain. After a specified number of cycles, it replenishes a predetermined amount, This S replenishment is not effective with current developerfreplenisher formula~ions but very effective with this invention since more of the correc~
replenisher is used.
After development in the processing solution of the invention, the silver halide film is fixed, preerably in an acid fixer, and washed and dried in the usual manner~ If a processing maohine is used, these steps will be de~ermined by the machine.
The following examples are illustrative of lS the inventionr wi~h Example 1 being the bes~ mode contemplated by the inventor of oarrying out the invention .
_ The following solutions were prepared in order to formula e a developer/replenisher ~I~
according to the present invention, and to sompare it wi h a conve~ional developer~replenisher In~redients ~g~
Part A
~ist. Water 250 Ethylenediaminetetraacetic 8 Acid (EDTA) Sodium Bisulfite (43% aq.) 333 30 ~ydroquinone 100 K~r 13 K0~ ~45% aq.) 323 ~2C3 (47% aq.) 116 Distilled Water to1 liter g Part B
__ Acetic Acid 560 Triethylene Glycol 240 5 Phenidone 60 5-nitroindazole 6.4
STABLE PHOTOGRAPHIC DEVELOPER
AND REPLENISHER THEREFOR
'le ~:
Thi~ invention is in the field of photographic silver halide developer solutions and replenishers therefor, and is specifically dir~c~ed to developer~replenisher solutions useful in low through-put machine processing (developing) of 10 photographic film.
8ao k~ound Ar t:
The use of so-called "automatic processors"
is conventional for developing imagewise exposed 5ilve~r halide elements such as ~-ray f ilms . The 15 exposed ilms are fed into the processor from a sa~eli~ht area~ i.e. one in whi~h the level of light is reduced below that which exposes th~ film further~
and is transported through various chambers containing the developer, the fixer and the water 29 washes. At th end of the processor, the film. is dried and exits into normal light as a finished ~product ready for use. This is illustrated in U.SO
Pat~nt 3,545,971 "Rapid Proce~sing of Photographic X-ray Film" (1966). This system is rapid and 25 convenien~ and large numbers of films can be routinely handled in this manner over long periods of time without dele~erious effec~s to the finished image. Of cou~set the processing solutions become exhausted by the passage of the exposed silver halide film and replenishmen~ mus~ be made to account for ingredient loss. Addi~ionally, the processing flui~s, especially the developer solution, are degraded aerobic~lly by contact with air and anerobically when simply left for long periods of P~-1810 35 inaction.
'~
When large amounts of ~ilm are being processed (high throughpu'c), exhaustion of ~he developer is due almost entirely to devalopment s~f the s ilver hal ide image . The developmen ~ reaction as 5 shown in Mason's "Pho~ographic Processing Ch~mis~xy"
Focal Press (1966~ page 74, is~
2AgBr ~ H2Q + Na2S03 ~ 7Ag ~ ~Br ~ NaBr + ElQS03Na Thus, some materials, i.e., hydroquinone and sulfite are lost while bromide, acld, and hydroquinone 19 mono~ulfonate are formed~ Also, no~ shown by this reaction, antioggant may be los~. Curren~ devPloper replenishers are formulated based on this reaction as follows: The replenisher is made higher in pH ~han developer and contains no bromide t SO as to offset the acid and bromide released by the development reaction. ~he other ingredients are se~ at concentrations whirh allow for ~he ~xpec~ed losses, the hydroquinone being offset by ~he antifoggants, without substantially affecting the sensi~ometry. In 20 this situation a replenishment rate can be co~veniently calculated ba~ed on the approximate area of film fed into the processor.
The other situation presen~s a more difficul t problem because when only small amounts of ~ilm are processed (low throughput), the developer deteriorates primarily from air oxidation and thermal reactions r and not from development reaction; Mason's ~Photographic Processing Chemistry~ supra at page 73:
2Q a~ 3 2 ~ HQS03Na ~ NaO~ ~ Na2S04.
That is, hydroquinone and sulfite are lost bu~ not bromide. Also, p~ increases, not decreases as in the development reaction. Also, since film passage activates the replenishmen~, low throughput decr~ases replenishment.
Current practice is to compensate for low throughput by increasing replenishment rate significan~ly e.gO~ as much as two-fold. This, however, can actually accelerate the problems caused by low throughput processing and cause sensitometric instability~ ~ does so because the replenisher, which is being added, in ~xcess, has higher p~I than the developer and no bromide. The effec~ of this is to (1) maintain the increasiny p~ of the developer 10 caused by oxid2tion, and (2) dilute the bromide content to levels so low as ~o cause sensitometric instability, reflected mainly in fog ~nd speed~ The presen~ inven~ion provides a replenisher formula~ion whieh is aimed at compensating for developer changes caused by nonuse, and not by the development reaction. Thus, ~he replenisher is characterized by a p~ lower ~han ~ha~ of ~he developer, and it contains the maximum amoun~ of bromide consistent with acceptable sensitometr.y. Now when replenishment occurs, pH will remain constant or slightly ~ecr~ase, the bromide will remain essentially constan , and the o~her changes will compensate as in state of the art formulations. Thus ~ by maintaining the developer composition more constant, the developer can maintain a useful lifetime e~uivalent to the high throughput processors.
I~ is accordingly an object of thls invention to provide an improved developer/-replenisher system for developing exposed silver 30 halide photographic filmO A further object is to provide a developer/replenisher sys-tem par~icularly useful for machine processing of X~ray film when low throughput s~f film is practised.
Summar~ of the Invention:
These and other objects are achieved in this invention by providing an aqueous processing solution useful as a photographic developer bath for automatic processing of silver halide photographic film, parti-cularly X-ray film, and as a replenisher therefor, consisting essentially of, per liter:
l-phenyl-3-pyrazolidone photographic developing 10 agent, or a derivative thereof 0.8 to 2.5 g Hydroquinone developing agent or a derivative thereof15 to 35 g Bromide ion 1 to 7 g Organic antifoggant and film speed restrainer 0.01 to 2.66 m mole Alkaline material and buffer to provide a pH of 10.0 + 0.3;
with the proviso that the replenisher solution will not only contain bromide ion but also will have a lower pH than tha-t of the developer solution.
Developers and replenishers made according to this invention can be used in processing machines for low throughput of X-ray film, for example, and will exhibit excellent stability over long periods of both use and nonuse. Hence, a further embodiment of the invention is a process for the automatic processing of exposed photographic silver halide X-ray film wherein the imagewise exposed X-ray film is developed in a photographic developer bath comprising a photographic developer, bromide ion, an alkaline material and buffer system to maintain the pH of the developer bath at a desired value, an organic antifoggant and film speed restrainer, and water; the developed X-ray film is fixed, washed and dried; and the developer bath is replenished by a ~J
replenisher solu~ion ts~ maintain constant the photographic properties o~ the developer bath during pro::essing of a large quanti~y o: exposed X~ray film~
characterized in that ~he processing solu~ion 5 described above serves as bo~ch ~he deveïoper ba~h and the replenisher ss:~lution; with ~he proviso that the la~ter have a pH lower 'chan ~hat of the developer.
Detailed Di~closure of ~he Xn~7ention:
The processing ~olu~ion of this inventior 10 can be used for both the develQper and the replenisher therefor~ In the lat~er embodiment, wherein the replenisher solution has a lower pH than ~hat of the developer, it is only necessary to add a small amount of acid, acetic acid, for example, to 15 ad~u~t the pH. However, for a commercial pu~-up~ a small amount of base (alkaline ma~erial~ is added to ~he develop~r to raise the pH of the developer rather ~han adding acid to the replenisher ~o lower its pH.
This will be illustra~ed in Example 1, wherein a 20 ~mall amount of base is added through the starter sol~ltion ~Part D). The replerlisher is added to the developer bath as needed, based on ~ime and/or the amount o film proc:essed, thus compensa~ing for both forms of developer exhausltion. It is surprising ~hat 25 this particular f ormulation can be used so successfull5~ for low throughput in automatic processors ~ince the di~erences b~tween it and the prior art are so slight. E~owever, as will be seen in the Examples, the difference in performance between the formulation of this invention and the prior art is very la~ge.
As the photographic developing agents in the processing solution, a combina~ion of l-phenyl-3-pyrazolidone (sold under the Ilford trademark Phenidone) or a derivative thereof such as 4-mel:hyl or 4 / 4-dimethyl phenidone, and hydroquinone or a derivative thereof such as chlorohydroquinone or bromohydroquir~ne is used. This combin~tion is parti~ularly suited fs~r automatic p~ocessing of X-ray 5 ilms, These ordinarily comprise a gelatins~-Ag33r, AgBrI, or AgClE~rI emulsion on a film support such as polyethylene ~erephthalate.
~ ny alka].ine material may be used to provide the required pH, such as sodium or potassillm 10 hydroa~ide~ sodium or potassium carbonatel etc. The buffer sysi:em may be any converlient systemy e.g., the borate and carbonate bu~fers conventionally used in X~ray developer baths are both suitable.
Th~ organic antifog~ant may be any organic antifoggant and film speed restrainer. Such organic antifoggants are commonly employed in X-ray developer baths and include compounds of the benzimidazole, benzotriazole~ benzothiazole, indazole~ ~etrazole, and thiazole groupJ as well as anthraquinone sulfonic acid salts. Two or more organic antifoggant~ may be used9 ~t is preferred to use a mixture of ~wo antifoggan~s such as 5 nitroindazole and benzo~riazole.
A range of bromide ion can be used successfully in this inven~ion and provides excellent stability. 1 to 10 g/liter of KBr, for example, will provide sufficient bromide ion. NaBr may also be employed. Optimum amounts depend on replenishment rate and specific formula.
These essential ingredients, when dissolved in water at the concentrations se~ f orth above, enable the photographic solution of ~he invention to function as a developer bath and a shelf-stable replenisher .
.
Other materials may be included in the processing solution, such as gelatin hardening agen~s, aerial oxidation res~rainers, sequestering agents, surfactants, dyes, etc., as well known in the art. See, e.g., U~S~ Patent 3,545,971 and ~Photographic Processiny Chemistry", supra, page 149 et seq~
Conventionally, all of ~he inyredients of the developer are prepared in con entrated form in water. Separate portions of the concentrates are furnished users so that interaction between ingredients is lessened while in ~hiq concentra~ed state. Then, the user makes up the developer solution by measuring various amounts from each part 15 and diluting with water to achieve the desired ~olu~:ion. The pH is then adjusted, e.g~, to 10~0 + 0. 3, and the soluticn charged ~o the.
p~ocessing tank~ e.gI, of the type described in U.S.
Patent No. 3,545,971, such as an "X Omat Processor"~
in the amount reguired by the system. Developm nt time is determined empirically or by the processor.
Replenishment will be carried out al: a rate per unit area of exposed ilm to provide processing of a large quantity of exposed film without change in ~5 sensi~ometric properties of the fi.~m, ~nd will be determined empirically, as is known. As a guide, when using an X~Omat Processor to process X-ray film, a suitable replenishment rate will be about 55 ml per 240 square inches o exposed ~ilm for development to normal radiographic density, usiny the processin~
solution o the invention.
Some processors have a standby replenishment mode. This works as follows: if no film is passed in a given time, the proc:essor goes into a standby mode which deactivates the drive train and dryer and reduces water supply. After a given time, it comes back on for several minu~es and then shuts off ayain. After a specified number of cycles, it replenishes a predetermined amount, This S replenishment is not effective with current developerfreplenisher formula~ions but very effective with this invention since more of the correc~
replenisher is used.
After development in the processing solution of the invention, the silver halide film is fixed, preerably in an acid fixer, and washed and dried in the usual manner~ If a processing maohine is used, these steps will be de~ermined by the machine.
The following examples are illustrative of lS the inventionr wi~h Example 1 being the bes~ mode contemplated by the inventor of oarrying out the invention .
_ The following solutions were prepared in order to formula e a developer/replenisher ~I~
according to the present invention, and to sompare it wi h a conve~ional developer~replenisher In~redients ~g~
Part A
~ist. Water 250 Ethylenediaminetetraacetic 8 Acid (EDTA) Sodium Bisulfite (43% aq.) 333 30 ~ydroquinone 100 K~r 13 K0~ ~45% aq.) 323 ~2C3 (47% aq.) 116 Distilled Water to1 liter g Part B
__ Acetic Acid 560 Triethylene Glycol 240 5 Phenidone 60 5-nitroindazole 6.4
2.66 m moles Benzotriazole 8.0 ~odium Bisul~ite (anhydr.~ 5 ~ Part C
~ist. Water 500 Glutaraldehyde (50~ aq.)300 Sodium Bisulfi~e (anhydrO) 106 Water.to 1 liter Part ~
Dist~ Water 500 2~ RO~ (45% a~O) 200 RBr 171 Water to 1 li~er To make developer Ir 2~0cc A
25cc B pH 10.2 25cc C
Water to 1 liter 23.4cc D
To make replenisher 250cc A pH 10.0 25cc B
30~5c~ C
Water to 1 liter For comparison, a conventional high throughput medical X-ray developer II was prepared. The most significan~ difference was that Part ~' ~of developer II) contained no K3r, and Par~ Dl contained 130 g acetic acid~liter instead of 200 y KO~(45% aq)/li~er.
~eveloper II had a pH of lO.lS, and replenisher II a p~ of 10.35 (compared to pH lO.0 for replenisher I).
In an ac'cual hospital situation, samples of 5 exposed, high speed medical X-ray film we.e proce~sed tca. 15-20 sheets of 8" x 10'i film/day) using developers I and II, ~hich were charged to a C~ONEX~
QC-l Medical X-ray Automatic Processor (E. I. du Pont de Nemol~rs and Company, Wilmington, DE). The respective replenisher solutions were supplied to the replenisher tank thereofO The activities of the systems wer~ checked by processing control strips of X-ray ilm exposed through a ~ 21-step wedge on Crone~ ~le~troluminescent (ELS) Sensitometer (E. ~. du Pont de Nemours and Company, Wi~mington, DE). Two st~ips per day (one in the morning and one in the afternoon) were processed and the sensitometry checked to see whether the processor and its solutions were performing well. Processing time (dry ~o-dry) w~s about 2-1~2 minutes at ~2~F. The processor was equipped with a conventional ammonium thiosulfate fixer solution.
In the case of developer/replenisher II, ~ above, high fog and lower speed was noted after about 2 weeks of use and the machine was shut-down and the solutions drained therefrom. In the case of developer/replenisher I, above, the fog and speed remained constant after more than 4 weeks of continued, low throughput use, demonstrating good long life performance.
Developer/replenisher I of Example l was operated for more th~n thirteen weeks at low throughpu~ at St. Josephls Hospital in Phoenix, Arizona in a Cronex QC-l processor under essentially 1~
~he same conditions as Example lo The same formula was also run over four weeks at high throughpu~, thus demonstrating that developer/replenishers of this invention exhibit excellent stability over long periods of time in both high and low throughput7 ~AMPLE 3 In order to differentiate this invention over another prior art developer/replenisher formulation, the example given in Mertz, U.S~ Patent No. 4,04~,571 "Processing Solution For Us~ As Photographic Developer Bath and Replenisher Therefor"
(1977), Col~. 3, 4 and 5 was repeated. In this reference, the organic antifoggant and film speed restrainer is defined as being betw~en 7-26 m mole/liter of solution; which compares to 2.66 m mole/liter in Part B of Example 1.
Corresponding Part B of th~ Mertz example containing
~ist. Water 500 Glutaraldehyde (50~ aq.)300 Sodium Bisulfi~e (anhydrO) 106 Water.to 1 liter Part ~
Dist~ Water 500 2~ RO~ (45% a~O) 200 RBr 171 Water to 1 li~er To make developer Ir 2~0cc A
25cc B pH 10.2 25cc C
Water to 1 liter 23.4cc D
To make replenisher 250cc A pH 10.0 25cc B
30~5c~ C
Water to 1 liter For comparison, a conventional high throughput medical X-ray developer II was prepared. The most significan~ difference was that Part ~' ~of developer II) contained no K3r, and Par~ Dl contained 130 g acetic acid~liter instead of 200 y KO~(45% aq)/li~er.
~eveloper II had a pH of lO.lS, and replenisher II a p~ of 10.35 (compared to pH lO.0 for replenisher I).
In an ac'cual hospital situation, samples of 5 exposed, high speed medical X-ray film we.e proce~sed tca. 15-20 sheets of 8" x 10'i film/day) using developers I and II, ~hich were charged to a C~ONEX~
QC-l Medical X-ray Automatic Processor (E. I. du Pont de Nemol~rs and Company, Wilmington, DE). The respective replenisher solutions were supplied to the replenisher tank thereofO The activities of the systems wer~ checked by processing control strips of X-ray ilm exposed through a ~ 21-step wedge on Crone~ ~le~troluminescent (ELS) Sensitometer (E. ~. du Pont de Nemours and Company, Wi~mington, DE). Two st~ips per day (one in the morning and one in the afternoon) were processed and the sensitometry checked to see whether the processor and its solutions were performing well. Processing time (dry ~o-dry) w~s about 2-1~2 minutes at ~2~F. The processor was equipped with a conventional ammonium thiosulfate fixer solution.
In the case of developer/replenisher II, ~ above, high fog and lower speed was noted after about 2 weeks of use and the machine was shut-down and the solutions drained therefrom. In the case of developer/replenisher I, above, the fog and speed remained constant after more than 4 weeks of continued, low throughput use, demonstrating good long life performance.
Developer/replenisher I of Example l was operated for more th~n thirteen weeks at low throughpu~ at St. Josephls Hospital in Phoenix, Arizona in a Cronex QC-l processor under essentially 1~
~he same conditions as Example lo The same formula was also run over four weeks at high throughpu~, thus demonstrating that developer/replenishers of this invention exhibit excellent stability over long periods of time in both high and low throughput7 ~AMPLE 3 In order to differentiate this invention over another prior art developer/replenisher formulation, the example given in Mertz, U.S~ Patent No. 4,04~,571 "Processing Solution For Us~ As Photographic Developer Bath and Replenisher Therefor"
(1977), Col~. 3, 4 and 5 was repeated. In this reference, the organic antifoggant and film speed restrainer is defined as being betw~en 7-26 m mole/liter of solution; which compares to 2.66 m mole/liter in Part B of Example 1.
Corresponding Part B of th~ Mertz example containing
3.6 g/liter of 5-chlorobenzotriazole and 5 g/liter of 5-nitroberlzimidaæole was diffi~ult to prepare and required heating to ca. 120F. Preparatian of the working strength developer/replenisher as described was also difficult and required constant heating to keep all the solids dissolved. For this reason the solutions could not be tested in a commercial, automatic processor. Instead, control strips of X-ray film were tray processed in this developer and took about 3 times as long to process as those processed in developer solution I of Example 1, above.
EXAMæLE 4 The following solutions were prepared:
:L~
~ mt . ~g ) Par t A
___ Dist~ WatercaO 3785 (1 gal3 EDT~ 75 Sodium Bisulfite 1428 EEydroquinone 946 KOH (45~ aq.~ 3075 KOEI (solid) 1383 Sodium ~icarbonate 315 ~Br 113 Dist. Water to 9. 46 li~ers (2.5 gals) Part B
Triethylen~ Glycol 402 ~cetic Acid 270 20 Phenidone 60 5-nitroinidazole 6 Benzotr iazole 8 Dist. Water to 1 liter Par t C
Water 50 0 Glutaraldehyde ~ 50% A~. )267 50dium Bisul~ite (anhydr . ) 106 Dis'c. Water to 1 liter A developer solution was made up as follows.
Dist. Water 26. 5 1.
( 7 ~a~ . ) NaBr 120 g Sodium Bisulfite (anhydr.) 270 g Potassium Carbonate (anhydr O ~ 312 g Sodium Carbonate 200 g ~?art A, above 4 . 75 1.
(5 quartsJ
Part B, a~ve . ~5 1.
(1 quar~) Par~ C, above O95 1.
~1 quart3 r~ist. Water to 37. 85 1.
(10 gallons) p~I ~û.17 ~ 0.05 Five gallons (approxd 19 liters~ of this developer wer~ charged to the processor described in Example 1. About 60 grams of ace tic acid were added 'co the 20 remaining 19 liters to give a pH of 10. 0 + O . 05 and this was used as the repl en1sher . The processor was also charged with standard ammonium thiosulfat~o fixer and seJc at 92F. Two samples of exposed X-ray f ilm (high speed CRONEX~4, E. I. du Porlt de alemours and 25 Compan~), 14 x 17 inch size t were processed (developed) and the sensitometry of ~he system checked with con rol strips as described in Example 1. The processor was then allowed ~o stand by for the remainder of the day. About 2, OOOCG of replenisher was added by the machine during this time. At the end of the B hour day, the machine was shutdownO The processor was run for 10 days in this manner. No substan~ial change was no~ed in the sensitome~ry of the con~rol strips used to check developer activity, indicatin~ that this formula was very sta~le to low throughput of silver halide film and resistant to anerobic and aerobic degradation.
The formula of Example 2 (p~ about 10.2) was used in this example, as both developer and replenisher, in the processor of Example l. Under low throughput conditions (7 to 10 sheets of X-ray film/day) i~ served for more than five weeks. At the end of this period of time, control strips processed in this machine showed that the activity of the developer was well within limits and produced excellent results. A conventional developer of the prior art deteriorates badly in less than two weeks under these conditions and re~uires shut-down and cleaning of the automatic processor followed by re-charging with fresh solution.
SUPPLEMENTARY DISCLOSURE
It has been found that in using the photographic processing solution of the present invention for automatic processing of X-ray film at low throu~hput of film and as a replenisher tharefor, best results, i.e., excellent fog stability and high control, are achieved when the organic antifoggant and film speed restrainer is present at a level in the range of from 0.01 to 6.0 m mole/literO Suppor-t for a range of 0.01 to 6.0 m mole/liter for the organic antifoggant and film restrainer is contained in the following examples, i.e., Examples 6 to 13 inclusive.
A developer/replenisher solution identical to that described in Example l was prepared, except that the level of antifoggant was increased to 5.32 m mole per liter (0.32 g/l of 5 nitro-indazole and ''~,~,.,~
0.40 g/l of benzotriazole). All other ingredierlts and conditions remained the same as described in Example 1. The activity of this solution was checked by processing control strips of medical ~ray pho-to-graphic film therein. Sensitometric results indica-te that this developer will perform satisfactorily under low throughput conditions, i.e., that this solution will remain stable for long periods of nonuse~
Example 6 was repeated e~cept that the level of antifoggan-t was raised to 7.0 m mole per liter (0.42 g/l of 5-nitroindazole and 0.53 g/l of benzo-triazole). Although film strips processed in this solution were satisfactory as regards sensitometry, solids precipitated from the solution. It was obvious from this fact that it would be impossible to keep this solution in an automatic processor.
EXAMPLES 8, 9 and 10 A developer/replenisher solution identical to that described in Example 1 was prepared except for the level of antifoggantO Three samples were prepared from this, and the antifoggant changed in each one as follows:
Antifoggant Level( ) Example m mole/l g/l 8 0.98 0.16 9 1.96 0.32 30 10 3.92 0.48 (1) 5-nitroindazole Film strips processed in these solutions were comparable, sensitometrically, to those processed 1~
in the preferred e~odiment, indicating that -these three levels of antifoggant will perform within this invention.
EXAMPLES 11, 12 and 13 A developer/replenisher solution iden-tical to that described in Example 1 was prepared, except that the level of antifoggant was changed as follows~
Antifoggant Level( ) 10 Example m mole/l g~r~
11 0.05 0.01 12 0.15 0.025 13 0.31 0.05 (2) 1-phenyl-5-mercaptotetrazole Sensitometric results indicate that this developer will perform satisfactorily under low throughput conditions, i.e., that this solution will remain stable for long periods of nonuse.
..
9~ ~
EXAMæLE 4 The following solutions were prepared:
:L~
~ mt . ~g ) Par t A
___ Dist~ WatercaO 3785 (1 gal3 EDT~ 75 Sodium Bisulfite 1428 EEydroquinone 946 KOH (45~ aq.~ 3075 KOEI (solid) 1383 Sodium ~icarbonate 315 ~Br 113 Dist. Water to 9. 46 li~ers (2.5 gals) Part B
Triethylen~ Glycol 402 ~cetic Acid 270 20 Phenidone 60 5-nitroinidazole 6 Benzotr iazole 8 Dist. Water to 1 liter Par t C
Water 50 0 Glutaraldehyde ~ 50% A~. )267 50dium Bisul~ite (anhydr . ) 106 Dis'c. Water to 1 liter A developer solution was made up as follows.
Dist. Water 26. 5 1.
( 7 ~a~ . ) NaBr 120 g Sodium Bisulfite (anhydr.) 270 g Potassium Carbonate (anhydr O ~ 312 g Sodium Carbonate 200 g ~?art A, above 4 . 75 1.
(5 quartsJ
Part B, a~ve . ~5 1.
(1 quar~) Par~ C, above O95 1.
~1 quart3 r~ist. Water to 37. 85 1.
(10 gallons) p~I ~û.17 ~ 0.05 Five gallons (approxd 19 liters~ of this developer wer~ charged to the processor described in Example 1. About 60 grams of ace tic acid were added 'co the 20 remaining 19 liters to give a pH of 10. 0 + O . 05 and this was used as the repl en1sher . The processor was also charged with standard ammonium thiosulfat~o fixer and seJc at 92F. Two samples of exposed X-ray f ilm (high speed CRONEX~4, E. I. du Porlt de alemours and 25 Compan~), 14 x 17 inch size t were processed (developed) and the sensitometry of ~he system checked with con rol strips as described in Example 1. The processor was then allowed ~o stand by for the remainder of the day. About 2, OOOCG of replenisher was added by the machine during this time. At the end of the B hour day, the machine was shutdownO The processor was run for 10 days in this manner. No substan~ial change was no~ed in the sensitome~ry of the con~rol strips used to check developer activity, indicatin~ that this formula was very sta~le to low throughput of silver halide film and resistant to anerobic and aerobic degradation.
The formula of Example 2 (p~ about 10.2) was used in this example, as both developer and replenisher, in the processor of Example l. Under low throughput conditions (7 to 10 sheets of X-ray film/day) i~ served for more than five weeks. At the end of this period of time, control strips processed in this machine showed that the activity of the developer was well within limits and produced excellent results. A conventional developer of the prior art deteriorates badly in less than two weeks under these conditions and re~uires shut-down and cleaning of the automatic processor followed by re-charging with fresh solution.
SUPPLEMENTARY DISCLOSURE
It has been found that in using the photographic processing solution of the present invention for automatic processing of X-ray film at low throu~hput of film and as a replenisher tharefor, best results, i.e., excellent fog stability and high control, are achieved when the organic antifoggant and film speed restrainer is present at a level in the range of from 0.01 to 6.0 m mole/literO Suppor-t for a range of 0.01 to 6.0 m mole/liter for the organic antifoggant and film restrainer is contained in the following examples, i.e., Examples 6 to 13 inclusive.
A developer/replenisher solution identical to that described in Example l was prepared, except that the level of antifoggant was increased to 5.32 m mole per liter (0.32 g/l of 5 nitro-indazole and ''~,~,.,~
0.40 g/l of benzotriazole). All other ingredierlts and conditions remained the same as described in Example 1. The activity of this solution was checked by processing control strips of medical ~ray pho-to-graphic film therein. Sensitometric results indica-te that this developer will perform satisfactorily under low throughput conditions, i.e., that this solution will remain stable for long periods of nonuse~
Example 6 was repeated e~cept that the level of antifoggan-t was raised to 7.0 m mole per liter (0.42 g/l of 5-nitroindazole and 0.53 g/l of benzo-triazole). Although film strips processed in this solution were satisfactory as regards sensitometry, solids precipitated from the solution. It was obvious from this fact that it would be impossible to keep this solution in an automatic processor.
EXAMPLES 8, 9 and 10 A developer/replenisher solution identical to that described in Example 1 was prepared except for the level of antifoggantO Three samples were prepared from this, and the antifoggant changed in each one as follows:
Antifoggant Level( ) Example m mole/l g/l 8 0.98 0.16 9 1.96 0.32 30 10 3.92 0.48 (1) 5-nitroindazole Film strips processed in these solutions were comparable, sensitometrically, to those processed 1~
in the preferred e~odiment, indicating that -these three levels of antifoggant will perform within this invention.
EXAMPLES 11, 12 and 13 A developer/replenisher solution iden-tical to that described in Example 1 was prepared, except that the level of antifoggant was changed as follows~
Antifoggant Level( ) 10 Example m mole/l g~r~
11 0.05 0.01 12 0.15 0.025 13 0.31 0.05 (2) 1-phenyl-5-mercaptotetrazole Sensitometric results indicate that this developer will perform satisfactorily under low throughput conditions, i.e., that this solution will remain stable for long periods of nonuse.
..
9~ ~
Claims (10)
1. An aqueous photographic processing solution useful as a photographic developer bath for automatic processing of X-ray film at a low through-put of film and as a replenisher therefor, consisting essentially of, per liter:
1-phenyl-3-pyrazolidone (photographic developing agent) 0.8 to 2.5 g Hydroquinone (developing agent) 15 to 35 g Bromide ion 1 to 7 g Organic antifoggant and film speed restrainer 0.01 to 2.66 m mole Alkaline material and buffer to provide a pH of 10.0 ? 0.3, and with the proviso that the replenisher has a pH
lower than that of the developer.
1-phenyl-3-pyrazolidone (photographic developing agent) 0.8 to 2.5 g Hydroquinone (developing agent) 15 to 35 g Bromide ion 1 to 7 g Organic antifoggant and film speed restrainer 0.01 to 2.66 m mole Alkaline material and buffer to provide a pH of 10.0 ? 0.3, and with the proviso that the replenisher has a pH
lower than that of the developer.
2. The processing solution of Claim 1, wherein the organic antifoggant is one or more members selected from the group consisting of a benzimidazole, a benzotriazole, a tetrazole, a thiazole and an anthraquinone sulfonic acid salt.
3. The processing solution of Claim 1, wherein the organic antifoggant and film speed restrainer is a mixture of 5-nitroindazole and benzotriazole.
4. The processing solution of Claim 1 which contains one or more adjuvants selected from the group consisting of gelatin hardening agents, aerial oxidation restrainers, sequestering agents, surfactants and dyes.
5. In the automatic processing of exposed photographic silver halide X-ray film wherein the imagewise exposed X-ray film is developed in a photographic developer bath comprising a photographic developer, bromide ion, an alkaline material and buffer to maintain the pH of the developer bath at a desired value, an organic antifoggant and film speed restrainer, and water; the developed X-ray film is fixed, washed and dried; and -the developer bath is replenished by a replenisher solution to maintain constant the photographic properties of the developer bath during processing of a large quantity of exposed X-ray film, the improvement which comprises using the processing solution of Claim 1 as both the developer bath and the replenisher solution, with -the proviso that the latter have a pH lower than that of the developer.
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
6. An aqueous photographic processing solution useful as a photographic developer bath for automatic processing of X-ray film at a low through put of film and as a replenisher therefor, consisting essentially of, per liter:
1-phenyl-3-pyrazolidone (photographic developing agent) 0.8 to 2.5 g Hydroquinone (developing agent) 15 to 35 g Bromide ion 1 to 7 g Organic antifoggant and film speed restrainer 0.01 to 6.0 m mole Alkaline material and buffer to provide a pH of 10.0 ? 0.3, and with the proviso that the replenisher has a pH
lower than that of the developer.
1-phenyl-3-pyrazolidone (photographic developing agent) 0.8 to 2.5 g Hydroquinone (developing agent) 15 to 35 g Bromide ion 1 to 7 g Organic antifoggant and film speed restrainer 0.01 to 6.0 m mole Alkaline material and buffer to provide a pH of 10.0 ? 0.3, and with the proviso that the replenisher has a pH
lower than that of the developer.
7. The processing solution of Claim 6, wherein the organic antifoggant is one or more members selected from the group consisting of a benzimidazole, a benzotriazole, a tetrazole, a thiazole and an anthraquinone sulfonic acid salt.
8. The processing solution of Claim 6, wherein the organic antifoggant and film speed restrainer is a mixture of 5-nitroindazole and benzotriazole.
9. The processing solution of Claim 6 which contains one or more adjuvants selected from the group consisting of gelatin hardening agents, aerial oxidation restrainers, sequestering agents, surfactants and dyes.
10. In the automatic processing of exposed photographic silver halide X-ray film wherein the imagewise exposed X-ray film is developed in a photographic developer bath comprising a photographic developer, bromide ion, an alkaline material and buffer to maintain the pH of the developer bath at a desired value, an organic antifoggant and film speed restrainer, and water; the developed X-ray film is fixed, washed and dried; and the developer bath is replenished by a replenisher solution to maintain constant the photographic properties of the developer bath during processing of a large quantity of exposed X-ray film, the improvement which comprises using the processing solution of Claim 6 as both the developer bath and the replenisher solution, with the proviso that the latter have a pH lower than that of the developer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28633181A | 1981-07-23 | 1981-07-23 | |
| US286,331 | 1981-07-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1181624A true CA1181624A (en) | 1985-01-29 |
Family
ID=23098119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000407806A Expired CA1181624A (en) | 1981-07-23 | 1982-07-22 | Stable photographic developer and replenisher therefor containing 1-phenyl-3-pyrazolidone and hydroquinone |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0071344B1 (en) |
| JP (1) | JPS5837644A (en) |
| AU (1) | AU554484B2 (en) |
| CA (1) | CA1181624A (en) |
| DE (1) | DE3268792D1 (en) |
| MX (1) | MX161751A (en) |
| NZ (1) | NZ201355A (en) |
| ZA (1) | ZA825244B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786584A (en) * | 1986-06-27 | 1988-11-22 | Fuji Photo Film Co., Ltd. | Method of supplying replenishing solution in automatic developing machine |
| US5187050A (en) * | 1986-11-07 | 1993-02-16 | Fuji Photo Film Co., Ltd. | Method for automatic processing of silver halide photographic material |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59214027A (en) * | 1983-05-20 | 1984-12-03 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material for x-ray photography |
| DE3431860A1 (en) * | 1984-08-30 | 1986-03-06 | Agfa-Gevaert Ag, 5090 Leverkusen | METHOD FOR PRODUCING COLOR PHOTOGRAPHIC IMAGES |
| JPH0679142B2 (en) * | 1985-10-18 | 1994-10-05 | 富士写真フイルム株式会社 | Development method |
| JPH0627932B2 (en) * | 1987-01-19 | 1994-04-13 | 富士写真フイルム株式会社 | Processing method of silver halide photographic light-sensitive material |
| US4794070A (en) * | 1987-06-09 | 1988-12-27 | Minnesota Mining And Manufacturing Company | Automatically processible photographic element comprising a non-silver halide layer containing bromide |
| JP2699003B2 (en) * | 1988-10-28 | 1998-01-19 | コニカ株式会社 | Processing method of silver halide photographic material |
| DE3938573A1 (en) * | 1989-11-21 | 1991-05-23 | Du Pont Deutschland | METHOD FOR DEVELOPING PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIALS |
| US8251100B2 (en) | 2008-03-19 | 2012-08-28 | Adma Elena Faraon Chaul Huerta | Needle-type stepped cylindrical stopper for automatic control of water consumption in pipelines |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3545971A (en) * | 1966-06-28 | 1970-12-08 | Eastman Kodak Co | Rapid processing of photographic x-ray film |
| AU456094B2 (en) * | 1971-05-15 | 1974-12-12 | Minnesota Mining And Manufacturing Company | New development composition for radiographic film |
| JPS5648864B2 (en) * | 1973-09-03 | 1981-11-18 | ||
| JPS5081539A (en) * | 1973-11-20 | 1975-07-02 | ||
| US4046571A (en) * | 1975-06-27 | 1977-09-06 | Gaf Corporation | Processing solution for use as photographic developer bath and replenisher therefor |
-
1982
- 1982-06-30 DE DE8282303437T patent/DE3268792D1/en not_active Expired
- 1982-06-30 EP EP82303437A patent/EP0071344B1/en not_active Expired
- 1982-07-22 NZ NZ201355A patent/NZ201355A/en unknown
- 1982-07-22 MX MX193692A patent/MX161751A/en unknown
- 1982-07-22 AU AU86296/82A patent/AU554484B2/en not_active Ceased
- 1982-07-22 JP JP57126859A patent/JPS5837644A/en active Granted
- 1982-07-22 CA CA000407806A patent/CA1181624A/en not_active Expired
- 1982-07-22 ZA ZA825244A patent/ZA825244B/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786584A (en) * | 1986-06-27 | 1988-11-22 | Fuji Photo Film Co., Ltd. | Method of supplying replenishing solution in automatic developing machine |
| US5187050A (en) * | 1986-11-07 | 1993-02-16 | Fuji Photo Film Co., Ltd. | Method for automatic processing of silver halide photographic material |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3268792D1 (en) | 1986-03-13 |
| EP0071344A1 (en) | 1983-02-09 |
| EP0071344B1 (en) | 1986-01-29 |
| NZ201355A (en) | 1985-03-20 |
| JPS5837644A (en) | 1983-03-04 |
| MX161751A (en) | 1990-12-20 |
| ZA825244B (en) | 1984-03-28 |
| AU8629682A (en) | 1983-01-27 |
| JPH0336204B2 (en) | 1991-05-30 |
| AU554484B2 (en) | 1986-08-21 |
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