, I 2,886,435 United States Patent Patented :May 12,1959

. 2,. coated with a colloid layer or composed of or surfaced with a porous water-absorbent or water-adsorbent sub 2,886,435 stance, such as paper, fabrics, regenerated cellulose, spongy-texture rubber, suitable plastic. compounds, natural PHOTOGRAPHIC IRON-SILVER COLORUPROCESS and arti?cial resins, cellulosic esters, etc. Michele P. L. Martinez, New York, N.Y., assignor, by A silver salt may be applied to ‘the layer after exposure. "mesne assignments, to Panacolor, Inc., Los Angeles, The ferrous ions that are formed,'image wise, by light ‘Calif., a corporation of Delaware action on ferric salt layers, act as reducing agents No Drawing. Application August 21, 1953 actually developers—of silver salts ‘that may be applied Serial No. 375,833 ‘ 10 to it in after-treatment. -' On exposure, the layers'so sensitized print-out in rich 2 Claims. (Cl. 96-49) dark brown to black, and they only need a’?rst rinse in water for 1 minute, then about 1 minute ?xing in 15% hypo, then a 5 minute wash. The silver image so ob The present invention relates to the photographic pro 15 tained is then treated in any of' the: known ways whereby‘ duction of monochrome and plurichrome pictures by color pictures can be obtained-namely by bleaching and means of light sensitive ferric salt layers and is character color-development, oxidation andv reduction processes, ized by the fact that at one stage or another of the toning, dye toning, ozobrome, dye imbibition, and the inherent procedure silver salts are brought into play re like. One detailed example of such color conversion pro sulting in the formation of silver images, the latter being 20 cedure will be given further on. afterwards transformed or converted into colored com The following are examples of ferric-‘salt sensitizers pounds or ,used to form colored compounds by way of intended to be treated with a silver solution after ex

accessory reactions. The iron salts are only intermediary posure: ' ' l ' means, while the color formations are truly based entirely The simplest formula, for application to base surfaces on silver. .. . 25 or to surfaces previously treated with a'substratum in An object of the invention is to providean inexpensive, tended to cause permanent ‘retention of a gelatine layer is: simple, rapid and fool-proof method of color picture production, and especially one which is compatible with Water _ cc 100 the conditions obtaining in processing laboratories han Gelatine ' L ' , gr__ 7 dling moving picture ?lm. , . .30 Ferric ______,....l______‘;-..gr-- 1.0 The various steps in the procedure and the sequence A more complex formula would be: of their performance, as applied to color ?lm production, form a new method of photographic colorprinting. Water ‘ ' cc ' 100 Having well in mind the fact that a pluricolor picture. Gelatine H I gr--. 10 35 Ferric __.._‘.._.._-______u_..gr__ 1S can only be obtained by a combination of several mono Ammonium oxalate _'-. ______'_....___gr_.. 2.50. chromes, and that the main application in view is, as stated, to moving picture ?lm processing, quite. a number Y..,__‘_. ______gr.._ 0.05 of conditions arise which ‘have to be ful?lled and which . An example of a formula for use to impregnate-.for place considerable restrictions on the choice of sensi instance, by immersion or by spraying--a water absorbent tizers most appropriate for the purpose. A chosen sensi 40 material or a gelatine coated surface, is similar to the tizer intended to be handled in ?lm, laboratory establish above, with the difference that the given quantities of ments must be: ‘ water are reduced in each case to 75 cc. and the gelatine is either entirely omitted or reduced to only ‘1 or_2> (1) Easily compounded grammes. An all-round improved formula would be: (2) Simple in coating , 45 (3) Of no critical temperature and atmospheric require Water ‘ M 100

ments ' - , ~ Ferric chloride - ‘ r ' - gr__ ' v3 (4) Preservable without particular care Oxalic acid ' ' ' gr__ 1.50 (5) Innocuous to underlaying, previously "j produced,‘ Ferric ammonium oxalate ______..gr..>_' 10 colored pictures -‘ g 50 Sodium oxalate _-______t. ____ ..'..____;_..gr'_’_ -' 2 (6) Call for treatments innocuous to previously pro Ferric ammonium'sulphate _-'_ .... -.' ______gr__ 1 - duced color pictures ’ The ferric sulphate and the oxalic acid are for contrast. (7) Neither strongly acid nor thoroughly alkaline in it A small amount of gelatine, one to two percent of the self nor in the treatments required water content, considerably enhances speed. , (8) Of great latitude in every direction 65 After exposure, in each case the material is immersed Only ferric salt sensitizers ful?ll at one and the same directly for 30 seconds up to 1 minute in a l, to 2% silver time all these conditions, with the added advantage that nitrate solution in distilled water. ‘ An improved silver the ultimate pictures obtained thereby are practically»; nitrate solution ‘for the purpose is: without any grain, or at least of an extreme ?neness of grain compared to other multicolor pictures produced, in 60 Water, distilled cc _ 100 any other way. Ferric salts require, it is true, a powerful Silver nitrate gr__ ’ 2’ source of light in exposure, but modern technical means Ammonia Q.s. are available that quite serve .the purpose; and, further (By q.s. is meant as much as required just to re-dissolve more, exposure can be effected during continuous travel the brown precipitate that is at?rst formed.) Then add: of moving picture ?lm and thus the exposure may be considered as a step in the processing sequence, just the Grams - same as coating, eliminating'thereby separate operation Sodium sulphite 0.15 Borax -' 0. 10 exposure, so called printing. , ' , 1 _ Ferric salts are preferably ‘used in water solutions, Immediately on application of the silver nitrate solution which can be compounded with suitable media as gelatine a vigorous image in, a rich sepia to black is formed: rinse and other colloids, gums, viscose and any other suitable for 1 minute, then ?x for ,1 minute in 15 to 20% hypo media, or can be vapplied plain to a support previously solution, then Wash for about 4 minutes. 2,886,435 3 . 4 a The silver image so obtained is thereafter treated, as I Step 4.—Bleach 1 minute in a solution of 100 cc. of in previous cases, so as to yield a coloreclimage in any water, 7 gr. of potassium ferricyanide, and 7 gr. of potas known suitable way. ‘ , sium oxalate neutral. Wash 2 to 4 minutes. Reverting to general characteristics of ferric ion sen Step 5 .—Immerse in a color developer compounded as sitizers, in repeated meticulous practices I have been able follows: 100 cc. of a sodium carbonate 2% water solution to ascertain three; novel points of considerable relevance: containing also 0.50% sodium sulphite: add to it 2 cc. (1) Gelatine layers seem endowed 1 of an in?nite of a 5% solution of diethyl-p-phenylene diamine hydro capacity to absorb and adsorb ferric ions time and again chloride in methyl alcohol, and 2 cc. of a 2% solution of over and over repeatedly, almost endlessly. I have ac p-nitro benzyl cyanide in equal parts of acetone and tually sensitized and resensitized the same piece of a 10 methyl alcohol. In 2 to 5 minutes the desired magenta ?xed-out moving picture ?lmas many as eight times, with image is formed. Wash 2 minutes, bleach 2 minutes in the production of a good strong image in every case, result same bleacher of step 4, rinse, ?x 2 minutes in 15% hypo, ing in as many as eight images on the same ?lm area. wash 4 minutes. (2) The speed to light of a gelatine-ferric salt sensitive Step 6.—-Wipe off surface moisture (no need to dry) layer increases with increase in the saturation of ferric 15 then immerse again (the same material) in sensitizer ions absorbed or adsorbed; 'hence, when a gelatine layer exactly as in Step 1 and dry correspondingly. has been made the recipient already of one color image, Step 7.—-Expose again the same material, so re-sensi there is physically: a reduced quantity or area of im tized, with the magenta image in register with the red pregnable colloid. This would cause a progressive re ?lter negative of the separation set. duction in speed of each impregnation, but can be com 20 Step 8.—-Repeat exactly step 3. pcnsated to a degree with increased saturation of ferric Step 9.--Repeat exactly step 4. salts in the solution used to resensitize. In practice, and Step 10.-—Repeat step 5 with the only modi?cation in the case of ferric ammonium oxalate, if in a ?rst im that, instead of the p~nitro benzyl cyanide solution men pregnation a 10 to 13% water. solution of the salt is used tioned, the same quantity (2 cc.) of a 5% solution of to produce a ?rst color image, in a second re-impregnation phenyl phenol sodium salt in methyl alcohol is employed. a‘22% solution of the same salt may be used, and in All operations as in the corresponding step. A cyan a third impregnation the saturation may then be 30% and image results, on top of the magenta previously formed. should be preferably added with up to 2% gelatine. Thus Step J1.—-Repeat step 6. exposures may be equalized, standardized or corrected, as Step 12.-Repeat step 7, using the blue ?lter negative the case may be, having. in mind also that the di?erent 30 of the separation set. elements of a set of color separation negatives may be Step 13.—Repeat step 8 (=3). of varied overall density so as to require adjustment. Step 14.—Repeat step 9 (=4). _ (3) At each impregnation, the ferric salts permeate to Step 15.-~Repeat step 10 (=5) with the further modi~ any part of the’laye‘r in which impregnable colloid is still ?cation that instead of the p-nitro compound and of the free or partly free for instance also, in part, underneath 35 phenyl phenol salt the same quantity (2 cc.) of a 5% a previously formed image. Everywhere the ferric salts solution of acetoacetanilide in methyl alcohol is used. so penetrate an image is thereafter formed. Hence my All operations as in the corresponding step. A ?nal mul~ resulting pluricolorirnages are not produced in strati ,ticolor picture is thereby obtained. ?cations but really are composed of e?ective mixture of Example II images, which, in projection, focus all on the same plane.‘ 40 This constitutes a considerable advantage on any other A release positive unexposed ?lm is printed in normal present color process, mostly pluri‘layers. This together way under a green-?lter negative of a separation set and with the absence of any discernible grain makes my developed ?xed and washed in normal way as in black process outstanding in its superiority, despite the fact and white procedure. The silver image is bleached in a that it is much moreeconomical. .45 suitable bleacher,.then washed, and then all the steps These points of speed increase, compensation and from 5 on are applied as in Example I. standardization are not embodied in the following general Example 111 examples, as they come of use only dependently on the particular qualities of the various negatives of a given A release positive unexposed ?lm is printed in normal separation set, while the, following examples are only in 50 Way under a green-?lter negative of a separation set and tended to give a clear full, description of average working then directly color-developed in magenta in a known way,

procedure, , t ‘ freed from silver also in known way, and ?nally washed. Exampleshere follow the whole procedure, step by Then all steps from 6 on are applied as in Example I. step, in extenso, for the production of a. multicolor mov Modi?cations in the order in which the images in the ing picture ?lm. 55 various colors are produced can be introduced as desired. Example I Duplicator materials, i.e. coated with plain gelatin or with silver halide emulsions on both sides, can be utilized, Step ].—A-Cellul0id‘ ?lm coated with plain gelatine with resultant shortening of the overall procedure inas (as may be obtained for instance, by ?xing out and Wash much as sensitizing baths and other general baths would ing well a positive ?lm acquired on the market) is im then operate at one and the same time on both sides, mersed for 1 minute in a solution made up of distilled applicators being resorted to only when diiferentiation of water 100 cc., and 15 gr. of ferric ammonium oxalate. agency (different color coupler) is demanded on each Nothing else is strictly necessary. The ?lm is then dried face. in a current of warm air, which takes only another Needless to say,’ considerable variations in quantities minute. ‘ I 65 and kind of ferric salts are possible in all ‘formulae. Step 2.‘-—Exp'ose the coated ?lm under the green ?lter From the above description it will be apparent to those negative of‘ a color separation set to a strong light rich in skilled in the art that the objects of this invention can ultra violet rays, which will require, according to the be accomplished in a number of speci?cally different ways strength of the light unit and the density of the negative, and I do not, therefore, desire to be limited to the illus~ from one to three seconds. 70 trations, but only as required by the appended claims. Step 3.-—Immerse for thirty (30) seconds ina 2% silver What I claim is: nitrate solution with su?icicnt ammonia added to dissolve 1. A process of producing colored picture ?lm which the brown precipitate ?rst formed and then add 0.15 gr. comprises‘ carrying out at least once the sequence of of sodium sulphite and 0.10 gr. of borax. Rinse 1 minute, steps comprising: sensitizing a ?lm with a solution con ?x in 15 to 20% hypo 1 minute, wash 4 minutes. sisting of water and ferric ammonium oxalate, exposing 2,sse,4ss the sensitized ?lm to light rich in the spectral region of a silver image in situ therewith, and removing the silver the ultraviolet through one of a set of color separation image. negatives, treating the exposed ?lm with a solution of silver nitrate to produce a visible metallic silver image, References Cited‘ in the ?le of this patent bleaching said silver image into a silver salt image, re developing said silver salt image with a color developer UNITED STATES PATENTS in the presence of a coupler to produce a dye image and 1,079,756 Fischer ______.. Nov. 25, 1913 a silver image in situ therewith, and removing said silver 1,126,495 Lewisohn ______Jan. 26, 1915 image. 1,225,146 Leighton et al ______.. May 8, 1917 2. A process for producing colored picture ?lm which 10 1,805,592 Omoto ______May 19, 1931 comprises carrying out at least once the sequence of 1,944,293 Martinez ______._ Jan. 23, 1934 steps comprising: sensitizing a ?lm with a solution con 1,945,772 Dassonville ______Feb. 6, 1934 slsting of water and a ferric ammonium double salt, ex 2,154,506 Hinman et a1. ______Apr. 18, 1939 posing the sensitized ?lm with light rich in the spectral 2,264,334 Schmidt ______.... Dec. 2, 1941 region of the ultraviolet through one of a set of color 2,444,567 Husek ______July 6, 1948 separation negatives, treating the exposed ?lm with a 2,509,232 Coote ______-_ May 30, 1950 solution of a silver salt to produce a visible metallic silver 2,750,292 Dippel et al ______._ June 12, 1956 image, bleaching said silver image into a silver salt image, redeveloping said silver salt image with a color developer FOREIGN PATENTS in the presence of a coupler to produce a dye image and 20 279,381 Great Britain ______Aug. 27, 1928