SE191663C1 - - Google Patents

Description

CLASS IN NTERNATIONAL SWEDISH G 03 c57 b: 18/08 PATENT AND REGISTRATION AGENCY Ans. 7482/1954 filed on 18/8 1954 posted on 27/1 1964 M P L MARTINEZ, NEW YORK, N.Y., USA Sat at. The present invention relates to multicolor photographic copying comprising depositing a layer of gelatin or an iron (III) sensitizer, consisting of one or more iron (III) salts, on a substrate. , exposure of the well-coated substrate under a negative with strong light to obtain iron (II) ions by the action of light on the iron (III) salts and treatment of the exposed substrate in a solution of a silver salt. The iron (II) ions thereby act as a reducing agent on the silver salt with the accompanying formation of a visible image of metallic silver.

The method according to the invention can be characterized in that the negative is a partial color negative and that the silver image is bleached into a silver salt image, sum is developed again with a color developer to obtain the corresponding partial color image or a silver image in situ, after which the silver image is aligned. sensitization tone in suitable solution, is exposed under another partial color negative and re-treated as above, that the various steps are repeated the required number of times and that the successive sensitizations are carried out while the substrate is still moist from the previous treatment.

According to the sacred patent specification 503 489, in the case of multicolor copying, a silver image and a color image are produced by means of physical color development based on different light-cantilever systems, whereby different partial color images can also be introduced in one and the same layer. As a light-sensing system, A-ven is called a sensitization solution with iron and silver salts. The color image is thus generated simultaneously with the metal image, which latter is removed, only after the color image has been obtained. As a result, there is no possibility of carrying out a check of and possible adjustment of the silver image before the color image is produced, which is a great inconvenience.

Dupl. at 57 b: 10; 57 b: 14/02; 57 b: 18/09 Furthermore, a study has been carried out, which shows the difference Indian work with jam and silver in the same, sensitization solution and with separate jam and silver solutions used one after the other. A film that had been sensitized with. the combined salts were exposed under a negative with a 6W ultraviolet jet emitter for 1 minute and then developed in water. The PA film obtained a very weak image. The same type of film which had been sensitized with a solution containing only the iron (III) salt was exposed under the same conditions and dipped in a 2% silver solution. Pregnant, a tat and ground silver image is immediately obtained. In the subsequent multicolor development, much better copies are further obtained in the application of the two-step process of the present invention than in the application of the known one-step process.

The iron (II) ions, which are formed by the action of light on the salt (III) salt layers, act as reducing agents or evoke the silver salts which are introduced into the layer through the post-treatment. The most effective iron (II) salts for this purpose are formed from the oxalate and sulphate, which, however, the joke can be used in sufficient quantity in the presence of gelatin. The double salts of iron and ammonium are very suitable. Addition of traces of ammonium chromate or potassium bichromate has a contrasting effect as well as small amounts of ferrous sulphate or oxalic acid.

The simplest composition of an agent for application to substrates or surfaces, which has first been treated with a sub-layer intended to permanently retain a gelatin layer is: water 100 ml gelatin 7 g jam (III) ammonium oxalate 10 g 2— - A rnera complex means are: water 100 ml gelatin 10 g iron (III) ammonium oxalate 15 g ammonium oxalate 2.50 g ammonium chromate 0.0 g A raw material which can be used, for example, for impregnation by dipping or spraying a water-absorbent material or a gelatin-coated surface is similar to the above described with the exception that the amount of water is reduced to 75 ml and the gelatin is reduced to only 1-2 g. An alimilute usable agent is: water 100 ml of iron (III) chloride 3 g of oxalic acid 1.50 g of iron (III) ammonium oxa. let 10 g of sodium oxalate 2 g of jam (III) ammonium sulphate 1 g of the jam (III) sulphate and the oxalic acid have been added with the male eye to contrast effect. A small amount of gelatin, 1-2 percent of the water content, increases the probability considerably. These silver-free sensitizers do not form any flag visible image on exposure or only a very faint image on the most strongly exposed parts.

After exposure, the material is whipped directly for 30-60 seconds in a 1-2% solution of silver nitrate in distilled water. A suitable silver nitrate solution for this andamal fir: distilled water 100 ml silver nitrate 2 g ammonia q.s.

(By q.s. is meant the great quantity which is required night and night for redissolution of the brown precipitate which is first formed). Then added: sodium sulfite 0.15 g borax 0.10 g Immediately after dipping in the silver nitrate solution, a sepia brown to black solid image is formed. The material is then rinsed for one minute, fixed for one minute in a 15-20% fixer sodium solution and washed for about 4 minutes. The silver image thus obtained is then processed, so that a color image is obtained.

Concerning the general properties of the (III) ion sensitizers, three new facts of considerable importance have been established by repeated, careful experiments: 1. Gelatin layers appear to have unlimited ability to absorb and adsorb dyes and the city unlimited number of times. The same piece of a final-fixed cinema film has been sensitized and desensitized as much as eight times during the formation of a good and strong image each time, so that one has received as many as eight images on the same image surface.

The photosensitivity of a photosensitive layer of gelatin and jam (III) salt increases with the matting of absorbed or adsorbed jam (III) ions. When a gelatin layer has thus received a color image, there is physically a reduced amount or surface of impregnable colloid. This could cause a kind of gradual reduction in the probability of each impregnation. However, this can be compensated to some extent by increasing the content of jam (III) salts in the laming used for renewal. sensitization. If a 10-13% aqueous solution of jam (III) is used in the first impregnation to form a first color image, a 22% solution of the same salt can be used in the second impregnation, while the content in the third impregnation can be 30%, the solution being suitably continued with 2% gelatin. The exposures can thus be equalized, standardized or corrected according to the need, whereby it should also be noted that the different elements in a series of color separation negatives can have different average densities and therefore require adjustment.

During each impregnation, the iron (III) salts penetrate to each part of the layer, where the impregnable colloid is still free or partially free and thus also partially under a previously formed image. Everywhere the jam (III) salts penetrate in this way, an image is then formed. The multicolor images obtained according to the invention are thus not formed in layers but in fact consist of an effective mixture of images, such as projection. all focused 1 saunna plan. This entailed a considerable advantage in relation to mango_ hitherto color processes, which mostly work with several layers. This ratio together with the absence of any discernible grain means that the process according to the invention becomes extremely advantageous despite the fact that it is much cheaper than many other processes.

The increase in brightness, compensation and standardization is not affected in the following general examples, since these properties are only used in dependence on the special properties of the various negatives in a color separation kit.

The invention will in the following illustrate the following by a non-limiting example.

Example.

Step 1. A celluloid film with a layer of pure gelatin (for example obtained by fixing and carefully washing a purchased positive film) is immersed for one minute in a solution consisting of 100 ml of distilled water and 15 g of iron (III) ammonium oxalate. Strictly speaking, nothing else is needed. The filin is then dried in a stream of hot air, which only takes another minute.

Step 2. The coated film is exposed below the green filter negative in a color separation kit with strong light, which is rich in ultraviolet rays, which depending on the intensity of the light and the density of the negative takes 1-3 S.

Step 3. The film is immersed for 30 seconds in a silver nitrate solution containing ammonia, sulfa and borax according to the indicated formula. The film is then rinsed for one minute, fixed for one minute, in a 15-20% fixer sodium solution and finally rinsed for 4 minutes.

Step 4. The film is bleached for one minute in a lane of 100 ml of water, 7 g of potassium ferricyanide and 7 g of neutral potassium oxalate, after which it is separated for 2-4 minutes.

Step 5. The film is immersed in a color developer with the following composition: 100 ml of 2% aqueous solution of sodium carbonate containing Oven% sodium sulfite, 2 ml of 5% paralysis of diethyl-p-phenylenediamine hydrochloride in methanol and 2 ml of 2% solution of p -nitrobenzyl cyanide in equal parts acetone and methanol. The desired purple image is formed at 2-5 mm. The film is then rinsed for 2 min., Bleached for 2 min. in the same bleach as in step 4, rinse, fix 2 min. in a 15% fixer sodium solution and finally rinse 4 mm.

Step 6. The water on the surface is wiped off (drying superfluous), after which the film is immersed in the sensitization solution exalt as in step 1 and then dried on the same salt.

Step 7. The slightly sensitized material is re-exposed with the beaker corresponding to the root filter negative of the separation kit.

Step 8. Step 3 is repeated exactly. Step 9. Step 4 is repeated exactly.

Step 10. Step 5 is repeated only with the change that instead of the p-nitrobenzyl cyanide solution the same amount, 2 ml, of a 5% solution of phenylphenol sodium salt in methanol is used. All treatments according to step 5 are repeated. In this case, a bluish image is formed over the previously formed purple image.

Step 11. Step 6 is repeated.

Step 12. Step 7 is repeated using the blade filter negative filter set.

Step 13. Step 8 = step 3 is repeated.

Step 14. Step 9 = step 4 is repeated.

Step 15. Step 10, which is similar to Step 5, is repeated with the further modification that instead of the p-nitro compound and the phenylphenol salt the same amount, 2 ml, of a 5% Riming of aceto-acetanilide I methanol is used to obtain of a yellow image. All treatments are repeated in the same way in the corresponding steps. The same end result is a multicolor image.

The order in which the different color images Midas can be moclified according to 8nskan. Double-sided materials, ie. materials coated with pure gelatin on the back sides can be used with a corresponding shortening of the entire treatment, since sensitizing baths and other general baths act simultaneously on the back sides. Separate paving means are clearly used only when different effects are desired on each side, for example with different color couplers.

You can use different amounts and different types of iron salts in the different recipes.

Claims (7)

P at entansprak: Salt in multicolor photographic copying comprising dewatering a layer of gelatin and an iron (III) sensitizer, consisting of one or more iron (III) salts, on a substrate, exposing the well-coated substrate under a negative light to obtain air iron (II) ions by the action of light ph jam (III) the salts and treatment of the exposed substrate in a solution of a silver salt, the iron (II) ions acting as a reducing agent on the silver salt with consequent formation of a visible image of metallic silver, can be characterized by the fact that the negative Or is a partial color negative and that the silver image is bleached into a silver salt image, which is redeveloped with a color developer to obtain the corresponding partial color image and a silver image in situ, after which the silver image is removed, the layer anyo scnsibilis eras solution, is exposed under another partial color negative and treated again as above, that the different steps are repeated as required gt number of times and that the successive sensitizations are carried out while the substrate is still moist from the previous treatment. 2. Claimed according to claim 1, can & ray, that the output is Iran a cinema film, which Or coated with gelatin and one or more iron (III) salts as sensitizers and that exposure, treatment and resensitization, etc., is performed while the film is being fed and wandering frail one step to the other. 3. according to claim 1 or 2, characterized in that a color coupler is used together with the color developer. Salt according to claim 1 or 2, characterized in that exposure takes place with a light which is rich in ultraviolet rays. 5. Salt, according to claim 1, characterized in that the iron (III) salt concentration in the sensitizer solution is increased for habitual successive sensitization. 4— - 6. Mt according to claim 5, characterized in that a small amount of gelatin is fed to the sensitizer solution. 7. Film with a multicolor image composed of monochromatic elements without stratification and visible graininess, characterized in that it has been produced according to nAgot et al. Patent claims 1-6. Request publications: Patents from Belgium 503 489.