United States Patent (19) 11 Patent Number: 4,965,177 McLaen (45) Date of Patent: Oct. 23, 1990 (54) ACTIVATORSOLUTION WITH COLD IMAGE TONE-PROVIDING AGENT OTHER PUBLICATIONS G. Haist, Modern Photographic Processing, vol. 1, 75 Inventor: Donald F. McLaen, Rochester, N.Y. 1979, pp. 260-262, John Wiley and Sons, N.Y. 73) Assignee: Eastman Kodak Company, B/W Print Processing with the Kodak Royalprint Rochester, N.Y. Processor, 1980. 21 Appl. No.: 388,412 Operating the Kodak Royalprint Processor Model 417, Nov., 1984. 22 Filed: Aug. 2, 1989 Maintaining the Kodak Royalprint Processor Model 51 Int. Cl. ................................................ CO3C 5/29 4.17, Nov., 1984. 52 U.S. C. .................................... 430/405; 430/448; Primary Examiner-Paul R. Michi 430/486; 430/.490 Assistant Examiner-Janet C. Baxter 58) Field of Search ............... 430/405, 448, 486, 490, 430/965 Attorney, Agent, or Firm-Robert A. Linn 57 ABSTRACT (56) References Cited Potassium iodide (or a related iodide) when incorpo U.S. PATENT DOCUMENTS rated in an alkaline activator for use in a rapid access 2,607,686 8/1952 Current ............................... 430/370 processor using developer-incorporated, resin-coated 3,55,555 6/1970 Fassbender ......................... 430/370 paper, (i) produces a cold image tone in black-and-white 3,619,186 11/1971 Parsons ............................... 430/232 photographic prints, and (ii) maintains the image tone of 4,124,390 1 1/1978 Kohn ................................... 430/390 a large number of prints within a narrow image tone 4,436,805 3/1984 Iguchi et al. ........................ 430/248 range over a (one week or one thousand 8X 10 inch FOREIGN PATENT DOCUMENTS print) design life of the activator solution. 1801330, 4/1970 Fed. Rep. of Germany . 497481 12/1938 United Kingdom . 3 Claims, 2 Drawing Sheets U.S. Patent Oct. 23, 1990 Sheet 1 of 2 FIG. I FIG 2 U.S. Patent oct. 23, 1990 Sheet 2 of 2 4,965,177 - b. YELLOW O- B - IMAGE TONE AFTER SEASONING (NO TONER) to RED 2 3 N A- IMAGE TONE FRESH (NO TONER) FIG. 3 4,965,177 1. 2 large number of prints before the batch of chemicals is ACTIVATOR SOLUTION WITH COLD IMAGE replaced. Hence, the toner chemical must perform in TONE-PROVIDING AGENT substantially the same way, time after time, in a con stantly changing environment. One reason why the FIELD OF THE INVENTION environment is constantly changing is the buildup of This invention relates to processing black and white by-products of development produced each time the photographs. More specifically, it relates to the produc activator is used. Thus, the toner chemical must operate tion of such photographs (with a cold image tone) by a in the same way when there is no, little, some, or much rapid access processor. Thus, this invention relates to by-product (from the development process) available in image tone control in photographic prints made by an 10 the solution in which the toner is employed. Moreover, automated apparatus. The apparatus makes prints from toner chemical, and by-product(s) therefrom are carried developer incorporated, water resistant papers by the downstrean with each print. These materials should "activation' process. not harm the downstream operations. The invention provides new compositions of matter, Applicant set out to develop a system which would and methods for their use. 15 provide a cold image tone in black-and-white photo The invention is especially adapted for use with the graphic prints made (from papers which did not provide KODAK ROYALPRINT Processor, a product of the such a cold tone) by a high speed automated processor Eastman Kodak Company. (such as the aforementioned commercial unit). He also set out to develop a system in which the image tone BACKGROUND OF THE INVENTION 20 remained within a relatively narrow tone range over the The image tone of black-and-white photographic recommended useful life time of the chemicals used, i.e., prints made by an automated processor is dependent, at over a relatively large number of prints. During the least to some extent, on the paper employed and the course of his studies, it was discovered that incorpora number of prints made with the batch of chemicals tion of potassium iodide in the activator solution unex used. Prior to this invention, the image tone of a small 25 pectedly accomplished both goals. It is believed that initial number of prints for some developer incorpo this discovery provides a significant advance in the art. rated papers generally had a blue tone which, after about 25 or 50 or other such small number of prints, RELATED ART became noticeably warmer, i.e., more yellow. Further Applicant is unaware of any reference which sug more, prior to this invention, it had been noted that over 30 gests this invention. Thus, Applicant is unaware of any the useful life of the chemicals previously available, that prior art reference suggesting incorporation of a cold the image tone of the prints produced could vary some tone-providing agent of this invention in an alkaline what, and in a non-controlled fashion. In some instances, these operating factors may be activator for use in the preparation of black-and-white considered to be less than optimum. For example, if 35 photographic-prints by an activation process. He is also multiple prints of a machinery part or similar device are unaware of any reference suggesting the use of an ac to be made for some professional purpose, e.g., advertis tivator/tone providing composition of this invention in ing, or publicity, it may be desired by the customer to a rapid process for preparing the equivalent of about have an image tone which is more uniformly colder one-thousand 8X10 inch (20.3X23.4 cm) prints with than what was heretofore available. More specifically, the same batch of chemicals. the customer may wish to have the image tone remain G. Haist, Modern Photographic Processing, Volume 1, relatively constant within an acceptable range, over say John Wiley & Sons, New York (1979), page 260, dis about 1000 prints, so that each recipient of a print copy closes that potassium iodide is known as an anti-foggant. receives about the same print as every other recipient. In the paragraph bridging pages 260 and 261 it is stated; The present invention satisfies this need. 45 "Once the minimum point of solubility of silver bro Fast black and white photographic print processing is mide in potassium bromide solutions is passed, the silver achieved by the aforementioned commercial processor, bromide becomes more soluble because of the forma which has been on the market for some time. The pro tion of complex ions of silver and bromide. High con cessor is designed to process black-and-white papers centrations of potassium bromide, and potassium iodide that have a developer incorporated emulsion on a wa SO as well, have such a great solubility effect on silver ter-resistant, resin-coated base. In the processor, chemi bromide that such concentrated solutions may be used cals are used over and over again to produce a large to dissolve rapidly all the unused silver bromide in the number of prints. In other words, the processor uses a emulsion layer. The color of developed silver may be batch of processing chemicals until the operator re come warmer in tone when a considerable quantity of places them with another batch. During operation, a 55 potassium bromide is present in the developer.” small amount of activator solution is continuously In the paragraph bridging pages 261 and 262, and in the added. This replaced the small amount of activator first full paragraph on page 262 it is stated; which is lost with each print. It is currently recom "At low concentrations potassium iodide is also an mended that the chemicals be replaced after one week, effective fog restrainer. For shorter times of develop i.e., five days of use, or after they have been employed ment A. P. H. Trivelli and E. C. Jensen found the fog to make one-thousand 8x10 inch (20.3X25.4 cm) prints removing power of potassium bromide to be greater or the equivalent, whichever occurs first. than that of potassium iodide, but for longer times of Because of the use conditions associated with auto development potassium iodide had the greater fog-sup mated processors, development of a toning agent for pressing power. Potassium iodide forms the very insolu such devices is a difficult task. This is especially true 65 ble silver iodide when the potassium iodide reacts with when a high degree of uniformity and controllability of silver ions. In practice the quantities of potassium iodide image tone are among the objectives. For example, as added to the developer are less than those of potassium stated above, such a processor is designed to prepare a bromide. Quantities of potassium iodide greater than 4,965,177 3 4. 0.1% are rarely used because of the great retardation of tone-providing compound of this invention can main development and the difficulty in fixing out the silver tain the image tone within a desired cold tone range for iodide that is formed. about one-thousand 8X 10 inch (20.3X25.4 cm) prints, If both potassium iodide and potassium bromide are or equivalent. In this manner, the agent of this invention present in the developer, the restraining action is at first 5 allows the processor to produce a cold image tone, due primarily to the iodide. When the iodide is used up, within acceptable limits, throughout the design life of then the bromide is the restrainer. In this way develop the batch of chemicals provided for use in the appara ers may be compounded that exhibit equal restraint as tlS.