US 3867151 A
A monobath composition for the combined developing and fixing of silver halide photographic emulsions comprises four developing agents, one each selected from the following classes - (a) 3-pyrazolidones; (b) aminophenols; (c) dihydroxybenzenes; and (d) enediols - and a silver halide solvent. By varying the monobath temperature and the extent of agitation, the composition, without reformulation, is effective in producing satisfactory images with all film emulsions without film speed loss.
Claims available in
Description (OCR text may contain errors)
iinite States 1' tent 11 1 Kate  Assignee: Delaware Photographic Product lnc., Buffalo, NY.
 Filed: May 10, 1973 2'11 Appl. No.2 353,935
 US. Cl. 96/61 M, 96/66 R, 96/66.3  Int. Cl G03c 5/38, G03c 5/30  Field of Search 96/61 M, 66 R, 66.3
[5 6] References Cited UNITED STATES PATENTS 2,685,515 8/1954 Wilson 96/66.3 3,276,875 10/1966 Schwalenstocker.. 96/66 R 3,345,166 10/1967 Land 96/61 M 3,542,554 11/1970 McMurtray..v 96/61 M 3,615,440 10/1971 BIOOm 96/66-R 3,615,513 10/1971 H8181 81 8.1..... 96/61 M 3,730,716 5/1973 Land 96/29 R FOREIGN PATENTS OR APPLICATIONS 765,250 1/1957 Great Britain 96/61 M OTHER PUBLICATIONS Photo Lablndex, Morgan & Morgan, Inc. Publ., p. 3-231 3-233, I971.
Primary Examiner-Mary F. Kelley Attorney, Agent, or Firm-ClarenceA. O'Brien & Harvey B. Jacobson [57} ABSTRACT A monobath composition for the combined developing and fixing of silver halide photographic emulsions comprises four developing agents, one each selected from the following classes (a) 3-pyrazolidones; (b)
32 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to chemical compositions for the'combined developing and fixing of silver halide photographic emulsions.
2. Description of the Prior Art Compositions for the combined developingand fixing of silver halide photographic emulsions (monobaths) have conventionally employed numerous silver halide developing agents. Exemplary of these agents are l-phenyl-3-pyrazolidone (commonly called Phenidone, a registered trademark of Ilford Ltd.), 2,4- diaminophenol dihydrochloride (Amidol), hydroquinone and ascorbic acid. In addition, various combinations of these agents are well known for use in conventional developer formulations. Thus,-for example, U.'S. Pat. No. 3,276,875 teaches'the use of Phenidone in combination with each of hydroquinone, amidol-and ascorbic acid, individually, and with a mixture of hydroquinone and ascorbic acid. Monobaths have also employed combinations of the various well known developing agents, as shown, for example, in US. Pat. Nos. 2,875,048 and 2,751,300 (Phenidone-asc orbic acid), US. Pat. Nos. 3,240,603 and 3,232,761 (Phenidone-hydroquinone) and Canadian Pat. Nos. 670,962 and 682,111 (Phenidonehydroquinone and Phenidone-amidol). 1
However, every known monobath employing co mbinations of the aforementioned developers is a special purpose monobath in the sense that its composition is formulated to make it particularly effective in the de-.-
tory images therewith is substantially reduced. In his,
Monobath Manual at page 45, Grant Haist explains the inability of known monobaths to produce satisfactory results with more than one emulsion by noting that commercial monobaths are often compromise formulations that fail to give the best results possible with each film or paper and that the general-purpose monobath usually fails to please anybody but the uncritical." .7
Haist recognizes that there exists no single monobath capable of producing satisfactory results with all emulsions without reformulation. He suggests, at page 51, a general purpose monobath, the MM--] monobath, which supposedly produces satisfactory results with all films by adjusting the mono-bath pH for each film. While it is true that pH adjustments of the MM-l mono=bath with either sodium hydroxide or glacial acetic acid produce images having acceptable contrasts with various films, this can be accomplished only at the expense of speed loss. With the exception of Verichrome Pan and Royal-X Pan forwhich MM-l apparently works without adjustment, pH adjustment is accompanied by speed losses of from ato 1 stop.
SUMMARY OFTHE INVENTION It is therefore an object of the present invention to provide a monobath which is effective with all films and which require neither reformulation nor pH adjustment to produce satisfactory images.
It is another object of-this invention to provide a monobath-composition which is effective for developing and fixing all emulsions by suitable changes in agitation and temperature.
It is still another object of this invention to provide a process of developing silver halide emulsions by employing a single monobath composition and varying onlyagitation and temperature for each emulsion.
Other objects and advantages will become apparent from the following description and appended claims.
Briefly stated, in accordance with the aforesaid objects,'the present invention provides a monobath composition comprising fourdeveloping agents (a) a 3- pyrazolidone; (b) an aminophenol; (c) a dihydroxybenzene; and (d) an enediol and a silver halide solvent. Preferably, the developing agents employed are Phenidone, amidol, hydroquinone and ascorbic acid, respectively, and the silver halide solvent is sodium, potassium or ammonium thiosulfate or thiocyanate. In another embodiment, the present invention comprehends a process for developing and fixing silver halide film by contacting the film with an alkaline-monobath comprising a developing agent selected from each of the aforementioned classes and a silver halide solvent. By varying the monobath temperature and the extent of agitation, the monobath compositions of the present invention are effective in producing'satisfactory images on all film emulsions without film speed loss.
DETAILED DESCRIPTION OF THE INVENTION The present invention,in its broadest form, provides an alkaline monobath composition containing four developing agents and a silver halide solvent, which monobath is effective for all films by suitable changes I in agitation and temperature.
The silver halide developing agents employed in accordance with the present invention are selected, one
in which the R groups each represent various substitu-' ents such as hydrogen, alkyl or aryl groups. For example, R can be hydrogen, a group such as alkyl prefera bly containing from 1 to 4 carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not; and R R R and R5 can be hydrogen atoms, groups such as an alkyl group preferably of l to 4 carbon atoms, or an aryl group such as phenyl.
, l-phenyl-3-pyrazolidone (Phenidone) is the preferred member of the 3-pyrazolidone class of agents for developing agents use in the present invention. Phenidone is preferred because it is commercially available in large quantities while other known, related developing agents having similar structure and characteristics are not widely available. The following compounds are representative of 3-pyrazolidone silver halide developing agents which l7. l-m-acetamidophenyl-4,4-diethyl-3-pyrazolidone- 18. l-p-(B-hydroxyethylphenyl )-4,4-dimethyl-3- pyrazolidone l9. 1 p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone 20. 1 p-methoxyphenyl-4,4-diethyl-3-pyrazolidone 21 l-p-tolyl-4,4-dimethyl-3-pyrazolidone 22. l-(7-hydroxy-2-naphthyl)-4-methyl-4-n-propyl- 3-pyrazolidone 23. l-p-diphenyl-4,4-dimethyl-3-pyrazolidone 24. l-p-(B-hydroxyethylphenyl)-3-pyrazolidone 25. 1-o-tolyl-3-pyrazolidone 26. l-o-tolyl-4,4-dimethyl-3-pyrazolidone 27. 3-pyrazolidones as claimed in U.S. Pat. No.
3,284,200 of the general formula wherein Z is a divalent aliphatic grouping which, with the carbon atoms in 4 and 5 positions of the pyrazolidone ring, completes a five-membered or membered cycloaliphatic ring and R is an aryl group, e.g., phenyl or naphthyl group. Such aryl groups may be substituted with hydroxy, alkoxy, oxyalkyl, amino, substituted amino, nitro, sulphonic or carboxylic groups or halogen atoms. These compounds include, for example, 1-phenyl-4,5-tetramethylene-3- pyrazolidone, l-phenyl-4,5-trimethylene-3- pyrazolidone and l-m-chlorophenyl-4,S-tetramethylene-3-pyrazolidone.
The dihydroxybenzene silver halide developing agents which are useful in the monobath may be hydroquinone, resorcinol or pyrocatechol.
The preferred aminophenol (the term aminophenol" will be employed hereinafter as generic to amino substituted phenols, including diaminophenols) for use in the present invention is 2,4-diaminophenol dihydrochloride, commonly known as amidol. However, a
number of aminophenol compounds can be used in place of the amide] in the monobaths of the present invention. It will be appreciated, however, that amidol is the only member of the class that is manufactured and commercially available in quantity. Exemplary of the aminophenol silver halide developing agents which are useful in the present monobath are the following:
1. p-aminophenol 2. N-methyl-p-aminophenol 3. 2,4-diaminophenol 4. 2,4-diaminoresorcinol. 5. 6-methyl-2,4-diaminophenol 6. 5-methyl-2,4-diaminophenol 7. 4-amino-6-methyl-2-methylaminophenol 8. 6-amino-4-methyl-2-methylaminophenol 9. 5-dimethylamino-2-methylaminophenol l0. 1,2,4-triaminobenzene l l. S-methyl-l ,2,4-triaminobenzene' l2. 4-hydroxy, 2,4-diaminodiphenylamine 13. 4,2,4-triaminodiphenylamine l4. l,3-diamino-4,o-dihydroxybenzene It should also be appreciated that the acid salts of any of the foregoing aminophenol agents will likewise be suitable for use in the present monobaths.
The enediol silver halide developing agents which are useful in the present monobath include the following:
1. ascorbic acid 2. d-araboascorbic acid 3. reductic acid 4. enediols as disclosed in U.S. Pat. Nos. 3,615,440
and represented by the formula wherein R R R and R each are selected from the class consisting of hydrogen and the radical CH R wherein R is hydrogen or a monovalent organic radical, selected from the group consisting of amino, cyano, halo, hydroxyl, carboxyl, sulfonyl, alkyl, cycloal kyl, aryl of the benzene or naphthalene series and alkaryl of the benzene or naphthalene series, at least one of said R R R and R being CH R Tetramethyl reductic acid is one particularly useful enediol.
5. 2-oxytetronic acid 6. 4-aryl-2-oxytetronic acid 7. 4-aryl-2-oxytetronimide 8. isoascorbic acid The monobath also includes a silver halide solvent which imparts the fixing capability to the composition.
' Exemplary of suitable fixing agents are sodium, potassium and ammonium thiosulfates and thiocyanates.
Inorganic sulfites, such' as sodium or potassium sulfite, are utilized in their well-known role as preservatives for the developing agents. In addition, strongly basic compounds, such as sodium or potassium hydroxide, are employed in sufficient quantity to produce an alkaline composition pH in the range 9.5 to 10.75. Preferably the pH is adjusted to the range 9.8 to l0.3 and most preferably to'the range It) to 10.2. The composition also includes a restrainer and grain reducer such as sodium or potassium bromide.
Table 1 sets forth a broad embodiment of the monobaths of the present invention.
TABLE I INGREDIENT CONCENTRATION (g/I) Minimum Maximum 3-pyrazolidone l 5 dihydroxybenzene 8 l4 aminophenol A. .3 enediol 1 l0 alkaline agent 3 7 inorganic sulfite preservative 20 75 restrainer A 2 fixing agent 60 1 10 In addition, conventional antifoggants, grain reducers (e.g., LiCl or NaCl), solubilizers, stabilizers, toners, buffers, antioxidants, sequestering agents and antisludge agents may be used in the monobaths of the present invention. A particularly preferred grain reducer is sodium or potassium thiocyanate which may be incorporated in the monobath in amounts up to about 2 /2 grams per liter. A preferred antifoggant, which also serves as a grain reducer, is benzotriazole in minute quantities up to about 0.1 gram/liter. Whether or not ammonium thiosulfate is employed as the fixing agent in the monobath, it has been found to be a useful optional additive in quantities up to 3 grams/liter above any amount used as a fixing agent to increase development speed and to yield increased density images. It is also noteworthy that where hard water conditions prevail some flocculation may occur in the monobath. To remedy this it is desirable to include up to Zgrams of a water softener or water conditioner per liter of composition. Particularly preferred for this purpose is so dium hexametaphosphate, which may be provided as the commercially available product Calgon, manufactured by the Calgon Corporation.
A preferred form of the present invention is set forth The following examples are illustrative of preferred monobath compositions which have' demonstrated their effectiveness on Tri-X, Plus X, Verichrome Pan and Pan-X emulsions.
EXAMPLE I Phenidone 3 g/l Hydroquinone 10 g/l Amidol 1 g/l Ascorbic Acid 5 g/l NaOH 5.7 g/l N11250:; 30 g/l NaBr 1 g/l M 5 0 511,0 80 g/l Sodium hexametaphosphate 2 g/l H;() to make 1 liter pH 10.15
When Plus-X was processed with the monobath composition of Example I it was surprisingly observed that the film speed was increased. Specifically, density and contrast were so great that it was necessary to decrease EXAMPLE II Phenidone 3 g/l Hydroquinone 10 g/l Amidol 1 15 g/l v Ascorbic Acid 5 g/l NaOH 6 g/l Na SO- 50 g/l NaBr r g/l Na s O SH O 85 g/l Sodium hexametaphosphate 2 g/l 4)2 2 3 2 g/l Benzotriazole 0.05 g/l H O to make 1 liter pH 10.25
EXAMPLE Ill Phenidone 2% g/l Hydroquinone 10 g/l Amidol 1 V2 g/l Ascorbic Acid 7 -g/l NaOH v 6 g/l Na SO 30 1 g/l NaBr 0.5 g/l Na S O 5H O 80 g/l Sodium hexametaphosphate 2 g/l' KSCN 2 g/l H O to make 1 liter pH 10.25
Temperature has been found to have a profound effect on the relative rates of developing and fixing with the monobaths of the present invention. For example, it has been noted that as the temperature increases above F the rate of development is greater than the corresponding rate of fixation. However, as the temperature decreases toward and approaches 60F, the rate of development becomes less than the corresponding rate of fixation relative to the 70F values. While this type of response is noted with most monobaths, with the monobath of the present invention the response is sufficiently profound .to enable temperature to be effectively used as a control on monobath performance. When several monobath compositions within the scope of the invention were tested using Tri-X 35mm film, it was noted that thefilm showed a one to twofstop variation in density as the temperature of' the monobath varied between 65 and F. Furthermore, when Panatomic-X 35mm film: was processed using the monobath set forth in Example I, there was at least a onefstop difference in the film when processed at 67F compared to processing at 75F. 5
Moreover, contrary to the generally prevailing notion tion. However, all emulsionswere found to be responsive to agitation changes. This observation, together with the profound temperature effects on development and fixation rates hereinbefore described, can be com- 8 Post-hardening by rinsing the developed and fixed film for about 10-30 seconds with either an acid alum hardener or an aldehyde was found to yield excellent results, as shown in the following Examples which illustrate the use of exemplary hardener rinse solutions.
not only with the monobath of the present invention but with all monobaths. Not only does post-hardening give good hardening but it neither reduces emulsion speed nor decreases monobath shelf life.
bined to advantage in utilizing the monobaths of the present invention with all known emulsion films with- EXAMPLE Iv but need to adjust pH or to reformulate for each emulsion. I
To establish applicable temperature and agitation pa- Ringgi Potassium sulfate 2 g rameters for various emulsions a number of. monobath Sodium Bisulfate 5 g compositions within the scope of the invention were g f g ggg g tested under various conditions on 35mm Tri-X, Plus- X, Verichrome Pan and Pan-X and on 120 Tri-X, Plus- X and Pan-X. Table lll sets'forth the optimum process- EXAMPLE V ing temperature and time for each emulsion with the Exemplary ofa post-hardener concentrate is the folmonobaths of the present invention to achieveresults lowing composition similar to D-76 conventional development in terms of contrast and density range. In addition, Table Ill sets 88% Ethanolamine 140 g forth mean agitation modes for optimum performance fllcxid t A d 138 g of the monobaths with each emulsion. It w ll be apprefi a g g 80 g ciated that the agitation modes are not rigorous, un- Ethylene Glycol g varying criteria, but rather are guidelines which, if followed within about a 20 percent permissible variation, One ounce of the post-hardener concentrate diluted will yield consistently satisfactory results. with water makes 1 quart of rinse solution.
TABLE III FlLM FOR- TEMPERA- AGlTATlON TOTAL MAT TURE DEVELOP.
TRI x mm 68-70F 60sec then s sec/30sec 6 min. PLUS X 35mm 586lF 10 set: then 5 sec/60sec 6Vz-7 min. VER PAN 35mm 66-68F l5 sec then 5 sec/30sec 6 min. PAN X 35mm 7072F continuous 6 min. TRl X 120 6769F 30 sec then 5 sec/305cc 7 min. PLUS X 120 58-.6lF 10 sec then 5 sec/60sec 7% min. PAN X 120 oil-70F continuous 7 min.
Emulsion hardening when processing with mono- EXAMPLE/V1 baths has heretofore taken the form'of (a) prehardening the emulsion in a hardening solution, or (b) incor 85% glutaraldehyde 10 ml porating a hardener in the monobath. Neither tech- 40 z o e 1 liter nique has been found to be satisfactory. Prehardening is itself time consuming, requiring, for example, 90 seconds using the solution of U.S. Pat. No. Re. 26,601. In A glutaraldehyde post-hardener is effective but suffers addition, following prehardening a thorough rinsing is from the problem that it ages at a muchfa'ster rate than necessary to avoid prehardener carry-over into the other post-hardeners, which may last for years. monobath and contamination of'the monobath. Incor- It should be appreciated that the post-hardening soluporation ofa hardener into a monobath, whether by detions of Examples IV-Vl are merely illustrative of the sign or through inadvertence, as by carry-over, typinumerous hardening solutions which are suitable. For cally causes a loss of emulsion speed and shortens the example, virtually any known prehardening solution shelf life of the monobath. For example, upon incorcan also be used for post-hardening. In addition, known poration of an aldehyde hardener in a monobath a pH and temperature conditions for prehardening are slight discoloration of the monobath evidences an inalso satisfactory for post-hardening. creased rate of monobath oxidation with an attendant A particular advantage of the monobath composiloss in development capability. Moreover, break downtions of the present invention is the flexibility they of the aldehyde hardener itself in the monobath makes allow in commercial packaging configurations to insure it doubtful whether effective hardening can be prolonged shelf life. For example, in one embodiment achieved, particularly where the monobath is prepared the primary monobath ingredients, except for the alkaand kept on the shelffor 3 to 6 months. linity agent and the four developers, are provided in dry It has been found, contrary to some reported obserpowdered form. The alkalinity agent is a separately vations (see, Sasai and Mil, Studies on Photographic packaged aqueous concentrate and the developers are Monobaths Containing Posassium Thiocyanate, Photoprovided in powdered, pre-mixed form in a number of graphic Science and Engineering, Volume 8, No. 3, individual compartments, each compartment containpages 270-275 1964), that hardening following develing sufficient developer to activate, for example, 16 opment and fixation, i.e., post-hardening, is effective, ounces of monobath solution. To use such a configuration, the powdered primary ingredients are dissolved in about 48 ounces of water at 52C to form a concentrate having a shelf life in a tightly stoppered bottle of at least one year. To prepare and activate the monobath, the
TABLE 'IV NaOH aqueous concentrate. BASIC MIX 1 21. Sodium Sulfite 11. Sodium Bromide Base Mix 0. Sodium Thiosulfate Y d. Ascorbic Acid e. Amidol f. Hydroquinone g. Phenidone Base Mix Z Various configurations of the ingredients of Table IV are possible to contribute to the longevity of the packaged ingredients and assure freshness of the product to the ultimate user.
CONFIGURATION 1 The NaOH concentrate is added to 800 mls H O. Basic mix (2) is then added and when dissolved additional water is added to make 1 liter. Alternatively, Basic Mix (2) may beadded in increments to activate only a portion of the diluted NaOh concentrate. CONFIGURATION 2 t --The NaOh concentrate is added to 800 mls H O. Base mix (2) Y is then added and'the resultant solution stored'prior to use at which time it is activated by add ing Base mix (2') Z and H to make 1 liter. Alternatively, Base mix (2) Z may be added in increments to activate only a portion of the stored solution. CONFIGURATION 3 l The NaOh concentrate is added to 800 mls of H 0. Base mix (2) Y and ingredient (2)(d) are then added and the resultant solution is stored prior to use at which time it is activated by adding ingredients (2)(e) (2)(f) and (2)(g).and H O to make 1 liter. Alternatively, ingredients 2)(e), (2)(f), and (2)(g) may be added in increments to activate only a portion of the stored solutlon. CONFIGURATION 4 The NaOh concentrate is added to 800 mls H O. Base mix (2) Y plus ingredients (2)(d) and (2)(g) are then added and the resultant solution is stored prior to use at which time it is activated by adding ingredients (2)(e) and (2)(f) to the solution and H 0 to make 1 liter. Alternatively, ingredients (2((e) and (2)(1) may be added in increments to activate only a portion of the stored solution.
Thus the method, composition and packaging of this monobath provide a photographic worker with: (1) a monobath that produces a maximum of shadow detail and full emulsion speed; (2) a primary aqueous mixture that has a shelf life of at least six months to one year prior to activationjand- (3) a methodof activation that enables the worker to activate the solution only when he needs to process film ensuring a fresh solution. By varying temperature and agitation it is possible to process all commercially available camera films intended Ill for continuous tone photography without the need of pH adjustment or reformulating the monobath due to the inherent differences between different speed films.
While the present invention has been described with referenceto particular embodiments thereof, it will be understood that numerous modifications can be made by those skilled in the art without actually departing from the scope of the invention. Accordingly, all modifications and equivalents may be resorted to which fall within the scope of the invention as claimed.
What is claimed 'as new is as follows:
I. An aqueous composition for the combined developing and fixing of exposed silver halide photographic emulsions,.having a pH in the range 9.5 10.75, comprising the following ingredients in the weight proportion ranges indicated per liter of composition:
3-pyraz0lidone developer 1 to 5 grams.
8 to 14 grams,
% to 3 grams.
Enediol developer selected from the groupconsisting of ascorbic acid, d-araboascorbic acid, reductic acid, 2- ozytetronic acid, 4-aryl-2ozytetronic acid, .l-aryl?- ozytetronimidc. isoascorbic acid'and cnediols having the chemical structure represented by the formula wherein R R R and R are selected from the group consisting of hydrogen and the radical CH;R R is selected from hydrogen and a monovalcnt radical selected from the group consisting of amino, cyano,
halo, hgrtraryl, carboxyl, sul/on alkyl, c'ycloalh l.
aryl of the benzene 0r naphthalene series and alkaryl o/the benzene or naphthalene series, at least one 0] said R R R and R4 being the radical CH R Inorganic sulfite preservative 20 to grains.
Alkaline agent 1 to 10 grams 3 to 7 grams.
Restrainer 4 to 2 grams.
Fixing agent selected from sodium, potassium and 60lo grams.
ammonium thzosulfates and thincganmes.
2. A composition, as claimed' in claim 1, wherein said 3-pyrazolidone developer is selected from developing agents having the following chemical structure:
wherein R R R R and R are selected from hydrogen, alkyl groups containing from 1 to 4 carbon atoms and aryl groups selected from the benzene and naphthalene series.
3. A composition, as claimed in claim 2, wherein said 3-pyrazolidone is l-phenyl-3-pyrazolidone.
4. A composition, as claimed in claim 1, wherein said enediol is selected from tetramethyl reduction acid and ascorbic acid. i
5. A composition, as claimed in claim 1, wherein said 11 aminophenol developer is 2,4-diaminophenol dihydrochloride. I I
6. A composition, as claimed in claim 1, comprising the following ingredients in the weight proportion ranges indicated per liter ofcomposition:
3pyrazolidone developer 2 to 4 grams dihydroxybenzene developer 8 to l2 grams aminophenol developer V: to 2 grams enediol developer 3 to 7 grams inorganic sulfite preservative 20 to 75 grams alkaline agent 3 to 7 grams restrainer A to 1% grams fixing agent 70 to.95 grams.
7. A composition, as claimed in claim 1, wherein said dihydroxybenzene is hydroquinone, said 3- pyrazolidone is l-phenyl-3-pyrazolidone, said enediol is selected from the group consisting of tetramethyl reductic acid and ascorbic acid, and said aminophenolis 2,4-diaminophenol dihydrochloride.
8. A composition, as claimed in claim 7, wherein said inorganic sulfite preservative is selected from sodium and potassium sulfite.
9. A composition, as claimed in claim 7, wherein said alkaline agent is selected from sodium and potassium hydroxide.
10. A composition, as claimed in claim 7, wherein said restrainer is selected from sodium and potassium bromide.
11. A composition, as claimed in claim 7, wherein said pH is in the range 9.8 10.3
12. A composition, as claimed in claim 7, further including at least one of the following additional ingredients: I
a. up to We grams perliter of a grain reducer selected from sodium and potassium thiocyanate;
b. up to 0.1 gram per liter of benzotriazole;
c. up to 3 grams per liter of ammonium thiosulfate;
and cl. up to 2 grams per liter of a water softening agent.
13. A composition, as claimed in claim 12, wherein said additional ingredient is a grain reducer selected from sodium and potassium thiocyanate.
14. A composition, as claimed in claim 12, wherein said additional ingredient is benzotriazole.
15. A composition, as claimed inclaim 12, wherein said additional ingredient is ammonium thiosulfate.
16. A composition, as claimed in claim 12, wherein said additional ingredient is a water softening agent.
17. A composition, as claimed in claim 15, wherein said water softening agent is sodium hexametaphos- 18. An aqueous compositionfor the combined developing and fixing of exposed silver halide photographic emulsions comprising the following ingredients in the weight proportions indicated per liter of composition:
l'-phenyl- S-pyrazolidone 3 grams Hydroquinone 10 grams Amidol 1 gram Ascorbic Acid 5 grams Na SO 30 grams NaOH 5.7 grams NaBr 1 gram Na s o 80 grams Sodium hexametaphosphate grams.
'19. A process for simultaneously. developing and fixing an imagewise exposed silver halide emulsion com- 'dihydroxybenzene prising contacting said emulsion with an aqueous monobath composition having a pH 'in the range of 8 9.5, said monobath comprising the following ingredients in the weight proportion ranges indicated per liter of composition:
3-pyrazolid0ne developer 1 to 5 grams.
8 to 14 grams.
% to 3 grams.
Enediol developer selected from the group consisting of ascorbic acid, darab0ascorbic acid, reduetic acid, 2- orytetronic acid, .l-aryl-E-oxyletronic acid, .l-aryl-Q- oz letronimide, isoascorbic acid and cnediOZ-y having the chemical structure represented by the formula wherein R R R and R are selected from the group consisting of hydrogen and the radical C[IgR, R is selected from hydrogen and a monovalerzl radical selected from the group consisting of amino, cg arzo. halo, hyaroayl, carhoxyl, suljonyl, alkyl, cgclunlkgl. arr/l of the hcnlcne or naphlhalcnrseries and (ll/illl'j/l aflhe benzene or naphthalene series, at least Ill)! 0] said R H It and R4 being the radical CII I\;,.
1 to 10 grains lnorganic sullito preservative... 20 to grams.
Alkaline agent o 3107 grams.
Reslraincr to 2 grams.
Fixing agentselectcd from sodium, potassium and 60 to grams. am noniurn thiosul/ates and thiocyanates.
20. A process, as claimed in claim 19, wherein said 3-pyrazolidone developer is selected from developing agents having the following chemical structure:
wherein R R R R and R are selected from hydrogen, alkyl groups containing from 1 to 4 carbon atoms and aryl groups selected from the benzene and naphthalene series.
21. A process, as claimed in claim 19, wherein said is hydroquinone, said 3- pyrazolidone is l-phenyl-3-pyrazolidone, said enediol is selected'from the group consisting of tetramethyl reductic acid and ascorbic-acid and said aminophenol is 2,4-diaminophenol dihydrochloride.
22. A process, as claimed in claim 21, wherein said pH is in the range 9.8 10.3.
23. A process, as claimed in claim 21, further including at least one of the following additional ingredients: a. up to 2% grams per liter'of a grain reducer selected from sodium and potassium thiocyanate;
b. up to 0.1 gram per liter of benzotriazole;
c. up to 3 grams per liter of ammonium thiosulfate;
d. up to 2 grams per liter of a water softening agent.
24. A process, as claimed in claim 23, wherein said l-phenyl- 3-pyrazolidone 3 grams Hydroquinone 10 grams Amidol 1 gram Ascorbic Acid 5 grams Na SO 30 grams NaOl-l 5.7 grams NaBr v 1 gram Na s O SH O 88 grams Sodium Hexametaphosphate grams.
25. A process, as claimed in claim l9, further including the step of agitating said monobath to said emulsion. l
26. A process,'as claimed in claim 25, wherein said monobath temperature is in the range 60 72F.
27. A process, as claimed in claim 19, further including the step of rinsing the developed and fixed emulsion in an aqueous hardening bath.
28. A process, as claimed in claim 27, wherein sai hardening bath includes a silver halide emulsion hardener selected from acid alum and aldehyde hardeners.
29. A process, as claimed in claim 28, wherein said hardening bath comprises the following ingredients in the weight proportions indicated per liter of hardening bath:
Boric acid 5 grams Aluminum potassium sulfate 5 grams Sodium bisulfate 5 grams.
30. A dry mixture, all ingredients of which are adapted to be admixed and dissolved in water to pro- A dihydroxybenzene developer selected from the group consisting of hydroquinone, resorcinol and pyrocatechol;
An amlnophenol developer selected from the group consisting of nominaphenol, N-methyl-p-aminophenol, 2,4-dianzinphenol, 2,4-diamin0resorinethyl-Q-methglaminophenol, (Lamina-441ieihyl-2-meihylaminophenol, 5- dimeihylamin02-1):ethylaminophenol, l.24,-lriaminoherzzene, a-meih I- 1,2,4-triarninobenzene, .l-hgdroag, 2,.i-diaminodiphch lamina, 4,2,4-lriraininofdiphenylamine, 1,3-diarnina-4,T-aihgdroxybenzene, and the acid sails ereo An enediol developer selected from the group consisting of ascorbic acid, d-arabaascorbic acid, reductz'c acid, Z-ozytetronic acid, ,4-aryl-2-olgietronic acid, l-argl-B-orgtetrOnimide, isoascorbic acid and enediols having the chemical structure represented by the formula A fixing agent selected from sodium; potassium and ammonium thiosulfates and thiecganatcs. V
31. A dry mixture, as claimed in claim 30, wherein said dihydroxybenzene vis hydroquinone, said 3-/ pyrazolidone is l-phenyl-3-pyrazolidone, said enediol is selected from thegroup consisting of tetramethyl reductic acid and ascorbic acid and said aminophenol .is
.32. A process, as claimed'in claim 27, wherein said hardening bath comprises the-following ingredients in the weight proportions indicated per liter of hardening bath:
88% Ethanolamine 140 grams Boricacid grams Glacial acetic acid 140 grams Aluminum chloride 6H O grams Ethylene glycol 30 grams.