US1389742A - Colored image and process of producing the same - Google Patents

Description

'ored Images and Processes of Same, of which thefollowingis a ful-l, clear,

-UNITED STATES PATENT O FFlCE.

J'OHN I. CRAIBTREE, OF ROCHESTER, NEW YORK, ASSIGNOR TO EASTMAN KODAK COMPANY, OF ROCHESTER, NEW YORK, A CORPORATION OF NEW'YORK. I

COLORED nines AND rnoorss or PRODUCING No -Drawing To all whom it may concern: r Be it'known that 1 JOHN I. QRABTREE, a subject of the King of Great Britain, re-

siding at Rochester, in the county of Monroe and State'ofNew York, have invented certain new and useful. Improvements in C01 Producing the and exact specification.

y invention. relates to co raphic images and the production;

hereof.

ify the image bfaphotograiphic "picture. se f that a dye-Will be adsorbedthereon fin cor-t respondence with the. original image, 1 thus;

giving a colored imagehaving approxi-f mately thesameform and gradation as the original picture. The inorganic part of such colored picture -may be further treated .or removed. Flat or even tones may be simir larly changed into colored tints suitablefor light'filters or general light-modifying purposes. A flat or even tone'in the picture being but the image of an object having a flat or even tone.- Ishall use the word generically to include flattones as the more usual graded images.

The objects of my invention are to g well as will yield pictures-having good gradation,

that will not injure or impair the wearing. qualities of the product, that will producef Since images made up of silver particles;

suspended. '1Il gelatin are most commonly met with -in photographic practice, I.will

describe, as an example of my invention, its

application to a silver image. Generally these results, carry out such a pro s nd'zjg wy md run SAME.

Specification of Letters llatent. Patented Sept. 6,1921. Application filed May 2, 1919. Serial No. 294,343.

stated, I treat the original, a primary image,-

in such a bath orbaths that/1t is converted danting dyes, "esp eci ally acid dyes of' the al1Za Il11 series: 'Themethods which will be converted into acomplex cyanid of silver and iron. In my pre erred process this V gsalt is silver ferricyanld, but by the use of ore particularly it relates rtothe mbtdant f 111g of y nto in 'g n c' cb pb li hi. may be dispersed or distributed through ai.

other baths silver ferro' yanid may be obtain'ed. This image is then converted .into

one'of -a. complexcyanid of iron and this suitable transparent ediu in the fform of images. I For examp'laf-lifiayfadd' toor in-turhinto iron hydroxid This last is a transparent colloidal image and I is capable of adsorbing or .mordanting dyes, and If .into an iron salt, which is capable of mor preferred process. Algela'tin film in which a silver photographic image is present'f'is bleached. in the following bath at F.,

for about two minutes, whereby the silver is converted into OHCDf silver ferricyanid :q Potassium ferricyanid r uui'l .2igrams. Potassium permanganate .2 grams.

to; .4 C el v 1 Instead of theabove bleaching the hromic acid (10% ...After being;ble ed g ln' the, above bath .hefilm is waslie forgabouta' minute in water 'andathen "'nmiersed' the] following solution whichf'i'conv rts the }s'ilver ferricy- 'anid iniage into a blue image' ofa' complex cyanid of iron-together withsilver chlorid:

Ferrous sulfate 15 grams. Hydrochloric acid ,5 cc. I Water .to ,.100. cc.

-The'ab0ve mentioned'bath also has theeffeet that itdissolves a little manganese stain (manganese dioxid) which was produced'by the first named bleaching bath.

' After rinsing in water, the film is .now immersed ina 35% solution of sodium thiosulfate for about a minute, so as to remove the is again rinsed and then immersed in a 1% solution of sodium carbonate or of sodium or potasseum hydroxid. The action of this last named bath is to convert theblue image to a faint yellow image of iron hydroxid.

The film containing this image is now placed in the dye solution, and I have found that many dyes, particularly acid dyes of the alizarin series, will be mordanted to the image. The dye bath is composed of a 2% solution of the dye to which acetic acid or ammonia may be added. The following dyes are noted as giving typically good results.

Alizarin red S Alizarin orange Alizarin yellow 3 G Alizarin brown Anthracene blue When the bath contains 2% ammonia it gives the best results'with the above orange and yellow dyes. Ali'zarin red gives the best result when the bath contains 12% .acetic acid. The temperature of the bath may be varied within certain limits, butit is primarily a cold bath in which the gelatin does not soften. The usual working temperatures would be F. After having been dyed the film is washed for about -a minute to remove the excess dye, and it has been found that prolonged washing and exposure to light does not affect the dye tones.

It is possible to obtain a pure dye image after the dye is thus mordante'd by removing the iron hydroxid with a suitable solvent; and for this purpose I find a 2 per cent. solution of oxalic acid satisfactory. There is left avery transparent dye image. With some dyes it is found. that the color of the remaining image is at first somewhat altered, but it is restored to the proper shade by being submitted to running water for a short time.

In place of the bleaching bath first men- I tioned, the film containing a silver image may 45 be submittedto the following bath:

Potassium ferricyanid 10,000 grams. Ammonia (concentrated .89) 2 liters. 200 liters.

silver ferroeyanid. It is then washed and may be treated with the acid ferrous sulfate bath above mentioned, or with the following bath: a Ferric ammonium sulfate 2000 grams. Potassium bromid 1000 grams. Hydrochloric acid (concentrated) 400 cc. Water to 200 liters.

In either case it is followed by the sodium thiosulfate and sodium carbonate baths above mentioned.

Still a third method of toning is to submit the silver image-to the following bath or a similar one containing ferric ferricyanid in solution:

Potassium bichromate 5 grams. Ferric ammonium sulfate 250 grams. 70 Oxalic acid 600 grams. Potassium ferricyanid 200grams. Ammonium alum 1000 grams.- Hydrochloric acid (10%) 200 cc. -VVaterto 200 liters.

The image resulting from this bath is presumably one of unchanged silver, silver ferrocyanid and ferric ferrocyanid. The unchanged silver and silver ferrocyanid are removed in a bathof potassium ferricyanid and sodium thios'ulfate (the well known Farmers reducer). The remaining blue image may then be converted into an iron hydroxid image by a bath of sodium carbonate, causticsoda, or" the like.

While the desired results may be obtained by following the processes as indicated above without a knowledge of the chemistry in volved, it maybe of interestv to note the probable reactions which occur. The reaction between ferrous sulphate and hydrochloric acid in the bath containing them results inthe formation of ferrous chlorid. When the silver ferricyanid image-,obtained by the first bath, is submitted to the acid ferrous sulfate bath it is presumed that the reaction involved is given by the following equation:

A The silver chlorid thus obtained is removed into hypo and the action'of the sodium carbonate bath is presumed to be as follows:

It may be noted, however, that it is very questionable whether the ferrous ferricyanid image obtained is a permanent one, as it is He thought highly probable that the oxygen present in the wash water oxidizes it into the ferric condition, so that the image is either onle of ferric ferrocyanid or one of the mixed sa ts.

e If the silver ferrocyanid image is first obtained,'the acid ferrous sulfate bath in the presence of oxygen converts this to ferric ferrocyanid and silver chlorid.

When, however, the silver image is trans-- 0 formed directly into the complex cyanid of iron image, the reaction involved is sup posed to be as follows:

It is understood that in place of sodium carbonate other baths containing hydroxyl ions may be used, in particular-solutions of any of the carbonated or caustic alkalis of 1 0 the alkali elements, lithium, sodium, potassium, and the radical ammonium. Other baths containing ferrous ions tutedfor the acid ferrous sulfate bath.

The resulting image of colloidal iron hydroxid is transparent, and-the slight color present does not affect the dye image disadvantageously. The process which I have outlined as preferred is advantageous in that a film is not submitted to any bath which tends the gelatin, by virtue of a combination of the gelatin and iron. The ferrous ions do not appear to have this efiect,where as the ferric ions which are present in those baths which contain a ferric salt have a mordantingeffeet and there is a tendency for the dye to produce stained highlights in the dyed image. v I. Y The resulting colored film was found to be unimpaired in wearing quality, and, by attending to manipulate details given hereinabove, effects can be duplicated with certainty. The image is durable on prolonged exposure, either to water' or-light.-" Since the salts resulting in each re-action are formed substantially in correspondence or proportiontothe original image and since the dye is adsorbed substantiallylim proportion to the mordanting salt, the dyed image will have a gradation similar to that of the original image.

While I have outlined above the preferred methods of carrying out this process, it is understood that many changes may be'made and the proportions of ingredients may be varied within certain limits, and such changes are contemplated as being within the scope of my invention as defined by the following claims.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

l. The process of producing a colored image from a photographic image, which cons'ists in replacing at least a part of the original photographic image by an iron toned image and mordanting a suitable dye to the toned, image. I

2. The process o'f producinga'colored image from a silver photographic image, whic l consists in replacing at least a part of the' silver image by an image of an iron salt and I in treating said image with a suitable dye until sufiicient dye is mordanted thereby-to produce a colored image. p

. 3. The process of producing a colored image in: gelatin from a silver photographic image, which consists in replacing the si ver image by anironhydrom'd image and. in

mordanting a dye the iron hydroxid tim age. z I

4. The producing a transparent colored 'ima'ge in gelatinfrom ajsilverphotographic image, which con's'istsimtransmay be substito abnormally tan or harden graphic image in a forming the silver image into a colloidal iron hydroxid image and in mordanting theron an acid dye.

5. The process of producing a transparent colored image in gelatin from a silver photographic image, which consists in replacing at least. a part of the silver-image by a colloidal iron hydroxid image and in mordanting thereon at normal temperatures'an acid'dye of the alizarin series.

6. The process of producing a colored im age in gelatin from a silver photographic image, which consists in transforming the. silver image into an'image of a complex cyanid of silver and iron, transforming this image into one of a complex cyanid of iron, and then transforming this image into one ofiron hydroxid, and mordanting a dye upon the iron hydroxid. image.

7. The process of producing a mordanted dye image from a silver photographicimage that comprises replacing at least a part of the silver'image by an image of a complex cyanid of silver and iron, replacing at least a part of this image by one of a complex cyanid of iron, and bathing this in a solutlon of one of the carbonated or caustic alkalis of the alkali metals including ammonium, and then bathing the resultant image in a suitable dye.

8. The method of producing a transparent mordanted dye image from a silver photographic image in a gelatin film that comprises the transforming of the silver image into a silver ferricyanid image, then bathing it first in a solution containing ferrous ions,-and then in a solution containing hydroxyl ions and finally in an acid dye of the alizarin'series. 1

9. 'The process of producing a transparent 105 mordanted dye image from a silver photogelatin film, which process comprises bathing the film in a solution of potassium ferricyanid and an oxidizmg agent, then in an acid solution of ferrous sulfate, then in a solution of sodium thiosulfate and then in a solution containing hydroxyl ions, whereby an image of colloidal iron hydroxid is obtained, and then' bathing the film inan acid dye of theflalizarin 115 series at a temperature less than F; 10. The process ofproducing ina gelatin film a transparent mordanted dye image from 'a silver photographic imageywhi'ch comprises submitting the film containing the 120 silver image-to"abath containing potassium ferricyanid and an: oxidizing agent, then submitting it to a bath containing ferrous ions, then bathing it in a solution of sodium thiosulfate,' a'nd then in a solutio 'contain- 125 ing hydroxylv 'ionsf which transforms the image into one of colloidal iron hydroxid, and then 'mordanting an acid 'dye to the iron hydroxid image. I

11. Theprocess of producing a dye image 180 photographic image,

- parent dye image in gelatinfrom a silver photographic image, which consistsin replacing at least a part of the silver image byan image of colloidal iron liydroxid, treating-this image with a suitable acid dye until sufficient dye is mordanted thereby .to

produce a colored image and then dissolving the iron hydroxld in a solution of oxalic acid, leaving a dye image.

14. The method of transforming a silver photographic image into an. iron hydroxid image, which consists of submitting it successively to baths that transform it into a complex cyanid of silver and iron, then into a complex cyanid of iron and then into iron hydroxid.

15. The method of transforming a silver photographic image in gelatin into a transparent colloidal iron hydroxid image capable of mordanting dyes that consists in submitting the silver image to a solution of potassium ferricyanid and an oxidizing agent, then to an acid solution of ferrous sulfate, thento a solution of sodium thiosulfate and finally to a solution containing hydroxyl ions. 1

' 16. The method of transforming a silver photographic image into a colloidal iron hydroxid image, which consists in transforming it first into a silver ferricyanid image, then bathing ing ferrous ions, andthen transforming the resultant image into one of iron hydroxid.

17. A colored photograph comprising a dye image that has been mordanted upon an iron toned image. v

'18. A colored photographic image consisting of an iron toned and mordant dyed image. 19. A colored photograph comprising a colloid layer containing an iron toned image and combined therewith a selectively mordant dyedimage.

20. An article of manufacture comprising -a gelatin film. containing an image composed of anacid dye droxid. Y I

. 21. An article of manufacture comprising mordanted upon iron bya gelatin film containing a transparent pho- 7' it in a solutioncontaintographic image. of colloidal iron hydroxid having mordanted thereto an acid dye of the alizarin series.

day df April'191 9.

' JOHN I. CRABTREE.

Si ned at Rochester, New York, this 30th I