US 2875049 A
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STABILIZED PHOTOGRAPHIC DEVELOPERS FOR COLOR PHOTOGRAPHY Donald J. Kridel, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application November 5, 1956 Serial No. 620,194
1 Claim. (Cl. 96 -66) No Drawing.
Thisinvention relates to developers for colorphotography which have been stabilized by the addition of. 1,3-diamino-2-propanol tetracetic acid thereto.
It has been previously proposed 'in developers in color photography to employ in conjunction with the usual color developing agent and the alkali metal sulfite, an hydroxylamine salt and an ethylenediarnine salt. However, it has been found that in some manner, as yet not completely understood, the alkali metal sulfite, hydroxylamine salt and ethylenediamine salt interact in solution, the result being that the eifective concentrations of the alkali metal sulfite and hydroxylamine salt become progressively lower upon storage even where the solution is carefully stopperedand free of contact wit air. Thus, there is a variable andunprediotalble "change in the sensitometric properties of such solutions upon storage, such as is customary in commercial processing ofcolor materials.
The aforementioned devolopin'g solutions are concerned primarily with the treatment of color materials having a coupling component present in the differentially sensitized layers for coupling with the oxidation products of the color developer.
It is, accordingly, an object of my invention to provide photographic developing solutions for color photography which can be stored for extended periods of time without substantial loss of the eifective concentration of the active ingredients. Another object-is to provide photographic developing solutions for treatment of differentially sensitized color materials containing coupling compounds in the sensitized emulsion layers. Still another object is to provide a method for making such solutions. Other objects will become apparent from a considerationof the following description and examples.
My invention provides a means of stabilizing photographic developing solutions of the type under consideration by the addition of 1,3-diamino-2-propanol tetracetic acid to the developing solutions. It has been shown in the art that this tetracetic acid derivative can be used in photographic developing solutions (U. S. Patent 2,656,- 273), although it was quite unexpected that this compound, which had been shown to be useful as a sequestering agent, could also be used to stabilize an otherwise unstable developing solution containing an alkali metal sullfite, an hydroxylamine salt and an ethylenediamine sa t.
By 1,3-diamino-2-propanol tetracetic acid, I mean the compound represented by the following formula HOOC-CH: OH OHzCOOH NOH2&'HCH2N HOOC-CHz CHtCOOH The tetracetic acid derivative employed in my invention is employed in combination with a phenylenediamine color developer which upon oxidation couples with the conventional coupling components employed in incorporated coupler photography. Such phenylenediamine developing agents include the hydrochloride or sulfate of N,N-diethyl-pphenylenediamine, N methyl p-phenyl enediamine, N,N-dimethyl-pphenylenediamine, Z-amino- S-diethylaminotoluene, 4-amino-N-ethyl-NJfi-methanesulfonamidoethyH-ni-toluidine, etc.
The amount of 1,3-diamino-2-propanol tetracetic acid added to the developing composition will vary somewhat, depending upon the particular developing agent employed and amounts of other ingredients present. In general, the concentration of the tetracetic acid can vary from about 0.2 g. to about 2.0 g. per liter.
The advantages of my invention can be illustrated as follows: An aqueous solution, designated solution A, was prepared having the following composition:
G. Sodium metaborate octahydrate 40.1 Sodium sulfite a 2.0 Color developer 1 i 4.0 Hydroxylamine sulfate a-.; 4.7
Ethylenediamine sulfate 6.5
Water to make one liter.
1 4-arnin0-N-ethyl N[l -methanesulfonamidoethyl] toluidine sesquisulfate monohydrate.
A second solution, designated solution B was prepared identical with solution A except that it contained 1.0 g. per liter of 1,3-diamino-2-propanol tetracetic acid. These two solutions were then stored for two weeks at 75 F., both in closed, tightly-stoppered bottles and in open con- Firm 24.11 959 tainers. By chemical analysis, the loss of concentration of sodium sulfite and hydroxylamine sulfatewas 'deter mined. r
. Loss in concentrationtz weeks storage) Closed Container Open Container Sodium Hydrox- Sodium Hydrox- Sulfite ylamine Sulfite ylamine Sulfate Sulfate Percent Percent Percent Percent Solution A 79 52 89 62 Solution B 12 22 20 26 A multilayer reversal color material of the type described in Yutzy and Van Campen U. S. application Serial No. 524,362, filed July 26, 1955, or a reversal color material of the type described in Meeussen and Bellay U. S.
Patent 2,673,800, was exposed in the usual manner to an appropriate subject. The exposed color film was then developed in a black-and-white developer for six minutes, the developer having the following composition:
G. Sodium hexametaphosphate 2.0 N-methyl-p-aminophenolsulfate 0.90 Hydroquinone 2.35 Sodium sulfite (anhydrous) 8.0 Sodium metaborate octahydrate 25.5 Potassium bromide 0.55 Sodium chloride 0.20 S-methylbenzotriazole 0.02
Thedeveloped material was then treated in a stop bath newsman for four minutes, the stop bath having the following com- I position:
Sodium d metate "22.0, Sodium bisulfi 2.7.0
Water to make one liter.-
The color material was then washed for eight minutes and subdued'room lights turned on after the washing had begun. seconds on each side at a distance of one foot from a No. 1 Photofiood. The re-exposed material was then color developed for four minutes in a developer of the type having the composition shown above and then treated in a second stop bath having the following composition:
G. Sodium bisulfi 12.4 Sodium diacetate 2 14.8 Sodiumacetate 6.5 Boric acid 7.5 Potassium aluminum sulfate 30.0
Water to make one liter. The material was then washed for three and one-half minutes and next treated in a bleach bath for eight.
bath having the following composiminutes, the bleach The material was then re-exposed for ten bath for three minutes, this particular Glacial acetic acid ml 10.0 Sodium thiosulfate (anhydrous) g 160.0 Zinc sulfate heptahydrate "g 5.0
Water to make one liter.
The material was then washed for seven minutes and dried for ten minutes. g
It is to be understood that the tetracetic acid stabilizing compound employed in my invention exists in the alkaline developing solutions in its ionized form. While an alkali tion:
Potassium ferricyanide 70.0 Potassium bromide 40.0 7
Water to make one liter.
The material was then washed for six minutes and treatedin a fixing bath having the following composition:
Sodium sulfite (anhydrous) Potassium aluminum sulfate.... g 13.4
be an alkali metal carbonate, such as sodium carbonate,- potassium carbonate, etc., or an alkali metal hydroxide;
such as sodium hydroxide, etc., in place of the metaborate salt illustrated above.
What I claim as my invention and desire secured by Letters Patent of the United States is: A photographic developing composition comprising an alkaline solution of 1,3-diamino-2-propano1tetracetic acid, sodium sulfite, hydroxylamine sulfate, ethylenediamine sulfate, and 4-arnino-N-ethyl-N-[B-methanesulfonamidoethyl]-m-toluidine sesquisulfate monohydrate.
References Cited in the file of this patent UNITED STATES PATENTS Gunther May'29, 1951 Henn et al Oct. 20,1953