US1411968A

US1411968A - Bleached and colored image and process of making the same

Info

Publication number: US1411968A
Application number: US230676A
Authority: US
Inventors: William V D Kelley
Original assignee: PRIZMA Inc
Current assignee: PRIZMA Inc
Priority date: 1918-04-25
Filing date: 1918-04-25
Publication date: 1922-04-04
Anticipated expiration: 1939-04-04
Also published as: FR540192A; DE378959C

Description

UNITED STATES PATENT OFFICE.

WILLIAM V. D. KELLEY, OF BROOKLYN, NEW YORK, ASSIGNOR TO PRIZMA, INCOR- PORATED, A CORPORATION OF MAINE;

BLEAGHED AND COLORED IMAGE AND PROCESS OF MAKING THESAME.

No Drawing. Application filed April 25,

T 0 all arbom it may concern:

Be 1t known that I. WILLIAM V. I). KELLEY, citizen of the United States. and resident of Brooklyn. in the county of Kings and State of New York. have invented certain new and useful Improvements 1n Bleached and Colored Images and Processes of Making the Same. .of which the following is a specification.

This invention relates to treating photographic images. and has for its object to enable the coloring of photographic images to be more accurately and easily accomplished than in processes heretofore proposed.

The invention is of especial use in the production of long strips of colored ima es for motion picture projection, such as isclosed in my Patent 1.259.411. issued March 12, 1918, but the invention is also applicable to plates, films, gum, and paper prints of various kinds, whether transparent or opaque.

The principal chemical processes for coloring images with which I am familiar obtain the color either by means of a metallic salt of the desired color, such as Prussian blue, known as toning, as in British Patent to Cox 15.648 dated June 30. 1914;. or by transforming the opaque silver of the image to a more or less transparent silver halid salt which will take up dye, as in Patent to Traube 1,093,503, April 1-1. 1914. or Miller 1.214.940, Feb. 6, 1917; or by treating the gelatine with potassium bichromate so that it will absorb dye where not hardened by light. Some single colors are satisfactorily obtained by toning, but not all, especially the reds which are desired to be combined with blue or blue green for natural color motion picture projection. In previous processes employing dyes mordanted by silver, the range of choice has been restricted to basic 1 .dyes because of the peculiar characteristics of silver halid as mordanting agents. Also, basic dyes are dichroic, that is they alter in color at different densities, and furthermore there are no known unmixed basic colors entirely suitable for complementary two or four color cycle projecting transparencies such as described in my aforesaid patent. It is characteristic of images bleached by the process of this invention that they do Specification of Letters Patent.

Patented Apr. 4, 1922.

1918. Serial No. 230,676.

not redevelop when treated with reducing agents. such as developers. Each of the foregoing processes has presented one or more difficulties. such as in proper balancing of color, degradation of color, as in washing to clear the whites, siri'ceone color of the mixture will often wash out faster than the other. thus changing the color entirely, prolonged time of treatment and delicacy of handling required, or lack of sharpness in color definition, all of which should be overcome in order that pictures in natural colors may be commercially produced with any black and white motlon picture projector.

This invention provides a process wherein acid and azo colors such as ponceaus, fast reds. .blues and greens. acid fuchsine, and yellows, now used in the wool dyeing industry, can be employed for dyeing photographic images, with the advantages of pro viding the necessary choice of pure, nondichroic colors, and complete transparency, fastness. brilliancy and sharpness of colored image in long lengths-of commercial film. The process starts with a black and white color value positive. which has been developed. and surplus silver halide removed by fixing in the usual manner. The coating is then hardened by immersion in a 10% formalin bath. and washed to remove excess of formalin. This sets the gelatine coating and renders it dye repellant or tends to prevent it from retaining the dyes. The image containing metallic silver is next treated with a bath which precipitates o 1' deposits a transparent insoluble metalhc mordant in situ with the silver, and in exact proportion thereto. This bath also changes the silver to a form, such as an oxide or halid, which can be dissolved out without afl ecting the transparent metallic mordant. The action of this bath is, I believe, to deposit a transparent salt of copper or of chromium, or salts of both, or a transparent double salt of copper and chromium, in and proportionate to the silver, since the lmage now has a brown color, possibly due to silver oxid, which color entirely d sap ears by treatment in the subsequent fixing ath, leaving no silver or silver compo nd In he residual transparent image. Atthe same time, the transparent copper or chromium compound is not affected either as to its transparency, or its character as a mordant.

The conversion bath preferably comprises potassium bichromate, 4.75 g.; potassium bromide, 9.5 g.; copper sulphate, 14 g.; hydrochloric acid, cc.; water 1000 cc. l\itric or acetic acid can be used instead of hydrochloric acid. This is a hot bath, of from 100 F. to 110 F., and only requires a few minutes. The .image, strip, plate or print, isthen treated in a fixing bath to dissolve out the silver oxide, halid, or other silver compound. This may be done after as well as before the dyeing, 15 without affecting the coloring. The fixing bath is an acid bath composed of sodium thiosulphate and sodium metabisulphite. After washin for five minutes, the image is ready for yeing, being now transparent and containing agents capable of fixing the dyes. At this stage, owing to the action of the conversion bath, the gelatin in situ with the original silver has probably been additionally hardened, so that the gelatin as a wholeis least absorbent to dye, and the transparent silver free mordanting image most absorbent to dye. This makes it easy to obtain brilliant whites and sharp contrasts in the final colored image.

The dye bath may vary in strength and temperature, but is preferably of about one half per cent strength at a temperature of from 110 to 130 About two minutes immersion willbe sufficient. The previous treatments of hardening and conversion have soaffected the coating that. even a steaming hot dye bath will not injure the film, nor affect the mordanting and dye absorptive qualities of the transparent copper, or other silver free compounds composing the ima e. Washing in hot water at about 120 for about three minutes will clear the dye from the whites without degrading or weakening the dyed image, which has the original sharpness, is as transparent as a pure dye image, and has the re uisite brilliancy of coloring.

n important feature of this invention is in its applicability to dyeing of photographic images, which increases strength, brilliancy and fastness of the color, and gives perfectly clear whites. I believe I am the first to dye positive transparent silverless images with acid or azo dyes.

I have found that acid and azo dyes, and particularly those used in wool dyeing, such as ponceaus, fast reds, blues and greens, fuchsine, and yellows, when mordanted and treated in accordance with this invention, furnish the necessary range of pure transparent colors, and preserve their color characteristics at all densities. It is important in making motion picture projecting transw parencies to use colors having these propphurous acid for brightening the color. This the erties, as they answer all commercial requirements. 1

An alternative method which gives good results is to employ a solution of sulcan-be put in the dye bath, or used as a dip after the whites have been cleared of dye by washing. The dye bath can be at a temperature of 70 F., and its working will sometimes be improved by the addition of 20 cc. of acetic acid for eachgram of dye. These colors may be in coatings on opposite sides of the support as in my patent aforesaid, the images in all cases preferably being registered by pins in the printing apparatus with reference to a predetermined perforation or perforations as a standard, as described in said patent. Also, both colors may be produced by this process, or three or more colors, so combined as to render complete color on each image area, or additively on successive image areas in projection as described in said patent. Reference is also made to said patent for directions as to handling double coated film in printing, and for protecting one color while applying the other, as all such details are fully illustrated therein and need not be repeated herein. 1

In thisspecification, where I say transparent, I mean that the deposit is of such character as to transmit light without substantial loss. although it does not necessarily have the same degree of transparency as the naturalpellicle or film. The transparent image of this invention before dye ing, can usually be faintly seen in transmitted light, and more clearlyv-in reflected light.

Vhile I prefer and specifically claim herein a process involving the production of a transparent silverless metallic.compound capable of mordanting acid dyes, together with the resulting undyed and hot dyed images, I do not restrict myself to any particular temperature or metal, nor solely to acid or azo dyes, except as required by the appended claims. Where the claims specify acid dyes, I intend to cover azo dyes as well without expressly so stating in the alterna- 115 tive form. The invention in its broad as pects is applicable to other uses than photography, and is not to be restricted to any particular use except as stated.

What is claimed is: 120

1. Process of treating a li ht exposed developed silver image in a coIloid carrier, which consists in bleaching said image with a bath which will produce an image capable of mordanting a dye and which will convert 2 the silver into a salt non-redevelopable by a developer.

2. Process of treating a light exposed developed silver image in a colloid carrier, which consistfiin bleaching said image with 130 a bath which will convert the silver into a salt non-redevelopable by a developer and which will produce an image capable of mordanting an acid dye.

3. Processwhich consists in treating a photographic silver image in a colloid carrier to deposit therein and in proportion to the density thereof a substance capable of mordanting a dye and to render the silver salt non-redevelopable by a developer, and in then dyeing the image to produce a colored image.

4. The process which consists in treating a photographic silver image in a colloid carrier to deposit therein and in proportion to the density thereof a transparent substance capable of mordanting a dye and to render the silver salt non-redevelopable by a developer, and in then dyeing the image to produce a colored image.

5. The process which consists in treating a photographic silver image in a colloid carrier to deposit therein and in proportion to the density.thereof a transparent substance capable of mordanting an acid dye and to form a silver salt non-redevelopable by a developer, and in then dyeing the image to produce an acid dye image.

6. The process which consists in treating a photographic image containing silver in a colloid carrier to form in situ with the silver a substance capable of mordanting a dye and to form a silver salt non-redevelopable by a developer. and in dyeing the mordanting substance.

7. The process which consists in treating a photographic silver image in a colloid carrier to deposit in situ with a silver salt a substance capable of mordanting an acid dye. and in dyeing the mordanting substance with an acid dye.

8. The process which consists in treating a photographic silver image in a colloid carrier to produce a silver salt non-redevelopable by a developer and to simultaneously deposit in situ with the silver salt a trans parent substance capable of mordanting a dye. and in dyeing the deposited substance.

9. The process which consists in treating a photographic silver image in a colloid carrier to produce a silver salt-non-redevelopable by a developer and to simultaneously deposit in situ with the silver salt a transparent substance capable of mordanting an acid dye. and in dyeing the deposited substance with an acid dye.

10. The process which consists in converting a photographic silver image in a colloid carrier into a soluble sllver compound by treating such image to'depositin situ with said silver compound. a transparent substance comprlslng a copper salt capable of -mordanting an acid dye, and in dying the copper salt with an acid dye.

11. The process which consists in hardening a photographic coating containing a developed silver image, in bleaching the image so as to be non-redevelopable in a developer and capable of fixing a dye, and in dyeing the image.

12. The process which consists in hardening a photographic coating containing a developed silver image, in bleaching the image so as to be non-redevelopable in a developer and capable of fixing an acid dye, and in dyeing the image with an acid d e. 13. The process which consists in hardening a photographic coating containing a; silver image, in treating the silver to form a transparent deposit capable of mordanting a dye and a silver salt non-redevelopable by a developer. in dyeing the transparent deposit, and in clearing the whites.

14. The process which consists in hardening a photographic coating containing a silver image, in treating the silver to form a transparent deposit capable of mordanting an acid dye and a silver salt non-redevelopable by a developer. in dyeing the 90 transparent deposit with an acid dye, and in A image. and in bleaching said image with a bath which will produce an-image capable of mordanting a dye and which will con vertthe silver into a salt non-redevelopable by a developer. v

16. The process of treating a light exposed developed silver image which consists in bleaching said image with a bath containing copper and chromium salts, which will form an image capable of mordanting a dye and which will react with the silver to form a silver salt non-redevelopable by a developer.

17. The process of treating a light exposed developed silver image which consists in hardening the emulsion containin said im- 11 age and in bleaching said image with a bath containing copper and chromium salts. which will form an image capable of mordanting a dye and which will react with the silver to form a silver salt non-redevelopable by a delevoper.

18. The process of treating a light exposed developed silver image which consists in hardening the emulsion containing said image and in bleaching said image with a bath containing copper and chromium salts. which will form an image capable of mordanting an acid dye and which will react with the silver to form a silver salt non-redevelopable by a developer.

19. The process which consists in con verting a photographic silver image in a colloid carrier into a silver compound nonredevelopable by a developer and in depositing in situ therewith a transparent com- 130 pound of a metal capable of mordanting a dye, and in dyeing the carrier in a dye capable of being fixed by saiddeposited compound. a

20. The process which Consists in converting a photographic silver image in a colloid carrier into a silver compound soluble in a fixing bath and non-redevelopable by a developer and in depositing in situ therewith a transparent compound of a metal capable of mordanting a dye, in dyeing the carrier in a dye capable of being fixed by said deposited compound, in clearing the whites, and in brightenin the dyed image.

21. The process which consists in dyeing a mordanting transparent image on a colloid carrier in a hot dye bath, and washing the image in hot water.

22. The process which consists in treating a photographic silver image in a colloid carrier to form both a transparent compound comprising copper and chromium salts capable of fixing a dye and a silver compound non-redevelopable in a developer, and in dyeing such transparent compound.

23. The process which consists in treating a photographic silver image in a colloid carrier to form both a transparent compound comprising copper and. chromium salts capable of fixing an acid dye and a silver compound non-redevelopable in a developer, and in dyeing such transparent compound with an acid dye.

24. A transparent photographic image in gelatin composed of a silver salt non-redevelopable in a developer and a salt of another metal capable of fixing a dye.

25. A transparent photographic image in gelatin composed of a silver salt non-redevelopable in a developer and a salt of 'an other metal capable of fixing an acid dye.

26. A transparent photographic image in gelatin composed of a silver salt non-redevelopable in a developer and a salt of cop per capable of fixing a dye.

27. transparent photographic image in gelatin composed of a silver salt non-redeto the latter.

29. A color image in gelatin composed of a transparent salt of a metal impregnated with an. acid dye.

30. A color image in gelatin composed of a transparent copper salt impregnated with an acid dye.

31. A color image in gelatin composed of transparent copper-chromium salts impregnated with an acid dye.

A colloid carrier having therein an image comprising a light insensitive nonredevelopable silver salt and a salt of another metal capable of fixing a dye.

33. A photographic image 1n gelatin comprising. a copper-chromium salt capable of fixing a dye.

34;. A photographic image in gelatin comprising a copper-chromium salt capable of fixing an acid dye.

35. A color image in gelat-in comprising a (gopper-chromium salt impregnated with a ye.

36. A color image in gelatin comprising a copper-chromium salt impregnated with an acid dye.

37. A color image in hardened gelatin composed of a transparent salt of a metal impregnated with an acid dye.

38. A color image in hardened gelatin 1 WiLLIAM v. D. KELLEY.