US1538816A - Color photograph or film and method of producing same - Google Patents

Description

May 19, 19z5 1,538,816

F. E. IVES COLOR PHOTOGRAPH OR -FILM AND MTHOD 0F PRODUCING SAME 5 lmaq Trler (Mod'died Product) INVENTOH A TTORNEYS.

CII

Patented May 19, 1925.

UNITED STATES EREDERIC E. IvEs, oE PHILADELPHIA, rENNsYLvAmA.

COLOR PHOTOGRAPH 0R FILM .AND METHODDF PRODUCING SAME:

Application iled February 15, 1923. Serial N'o. 619,187.

To all whom t may concern.'

Be it known that I, FREDERIC EUGENE IvEs, a citizen of the United States, residing at Philadelphia, in the county of Philadelphia and Sta-tev of Pennsylvania, have invented a cert-ain new and useful Color Photograph or F'ilm and Method of Producing Same, of which the following is a specification, reference being had therein tothe accompanying drawing.

This invention relates to color photographs or lms and method of producing same. The invention involves both the arts of color photography and motion pictures and constitutes an improvement in both arts. In its broad aspect the object of the invention is to afford a simple, effective and convenient mode of producing a multicolor picture or print, and one which will be less complicated and `quicker to carry out and yield a better product. More particularly, an object is to produce two, by which I mean at least two, dierently colored images, to be successivelyly produced and blended in the same member or carrier, thus obviating the necessity of attaching independently produced members. It is an advantage of the present invention that the images may be produced within the body of a single colloid layer, which is the plan refered to in my prior Patents Nos. 1,17 5,540 of February 8th, 1916, and 1,278,668 of' September 10th, 1918. The present invention improves and quickens the process 0f Said prior patents and affords a' superior resulting product These are some of the advantages and objects of the present invention, and further objects and advantages will be elucidated 1n the hereinafter following description or will be apparent to those skilled in the art.

' To the attainment of the above referred to objects and advantages the present invention consists in the novel processes, steps and products hereinafter described. First `will be described one or more embodiments of the invention', and thereafter the novel features will be pointed out in the claims.

Two or more simultaneously exposed views or series of views will be supposed to have been taken from substantially a single viewpoint for the purpose of securing color selection negatives from which afterward the positives or diapositives are to be made.

employed, for, although the three-colorv Sys- -ter'n might be used, the two-color is eminent- The two-color system will be supposed to be v ly more simple andis suficiently satisfacu tory" for general practical purposes.

In exposing for the View or series of views constituting the subject, there may be a red screen interposed in the path of thek light rays or in some other way a selection of the member from the green-representing negav tive, thus producing a silver image atthe interior side of the gelatin layer which afterwards was toned to a red color; and, subsequently, from the red-representing negative the second printing was performed at the exterior surface of the gelatin for producing a blue-to-green image. -One of the negatives, the first one, was a reversed negative so -that the two images, printed from opposite sides, would properly register. After the formation of the first or interior image, the gelatin layer was required to be resensitized for the printing of the second image. It was resensitized by the iron process, giving eventually the blue-to-green image oesired. The color toning of the first image was described as following the production ofthe second image. This process while efficient and giving good results was somewhat slow and 'therefore disadvantageous from a practical standpoint. Especially it was slow in regard to the steps of resensitizingy and. producing the second or exterior image. The present invention gives a much quicker'and more satisfactory procedure.

The present invention in part may be illustrated by diagrams. In the accompanying drawings showing one mode of'employing the principles of the present invention, Fig. 1 may be considered aside elevation of a red-representing negative facing downward.

' f Fig. 3 represents a sensitized colloid film Fig. 2 is a similar view of a green-representlng negative facing downward.

facing upward and on which the final picture is to be produced. l Fig. 4 illustrates the step of printing from the red-representing negative upon'the film. Fig. 5 on an enlarged scale is a sectional view of the film orprint after the production of the first image.

Fig. 6 is an elevation showing the ste-p lof printing from the green-representing negative to form the second .image in the film.

Fig. 7 is an enlarged section showing the- The present invention may be conven-` iently carried out in the manner which will now be specifically described.' Assuming the two-color system, we commence ith a set of color selection negatives 10 and 11. rlhe first negative 10 may, for example, represent the red components of the picture and the nega-tive 11 the green components. Eventually thew final picture will include a blue-to-green positive image from the first vor red-representing negative, and a reu `image from the green-representing negative.

The print or film 12 in which the positive images are to be formed and blended comprises colloid portions 13 supported preferably on a transparent or Celluloid carrier 14. The first step in the process is to expose by means of the first negative and form an image at one surface of the colloid portion of the print or film member 12. It is to be assumed that the colloid layer 13 is sensitiz'ed with silver haloid. The first printing is preferably by the red-representing negative 10, and, as shown in Fig. 4, this negative may be a reversed negative and used in such a way as to effect the exposure at the rear or through the carrier 14, so that the resulting image will be conned largely to that side of the gelatin layer which is next to its carrier, and may be referred to as the bottom or interior surface; but this exposure may alternatively be made upon vthe outer.

face, as later described.

Having been exposed, the silver image may be developed and will be found to extend into the exposed surface of the gelatin in a manner that will be roughly understood from the enlarged cross-section,l Fig. 5, in

which the colloid layer 13 is shown as hav-Y ing a silver image 15 at its'bottom side with a mass of gelatin 16 filled with silver bromid extending between the image and the top surface.

The general plan of the present improvement is to first produce an image 15 from the red-representing negative, as already stated, and then convert it to a blue-to-green image by any suitable steps such as those hereinafter described., This is contrary to said prior Patent 1,278,668 wherein the first image is produced from the green-representing negative and converted to a red colored positive. The next step of the present inventionis to convert or recouvert the silver ferrocyanid base of the 'converted blue print to silver bromid instead of dissolving it out or making it inertto light and development as has previously been proposed. Then .the first orblue-to-green image is produced by the iron toning or converting process a base of silver ferrocyanid remains, and hereinafter will be specifically described how this may be converted to silver bromid. The next operation is the production of the second image by the usey of the green-representing negative. The image is printed in the sensitivesilver bromid, and upon development gives normal graduations of density.v Fig. 6 shows this printing at the top or outer side, and Fig. 7 shows the second image 17 at the top surface of the gelatin; but it may alternatively be printed in the same face as the blue image, as .later described. Finally this second image is to be toned or converted to a red color, thus completing the process. The novel method thus described in general outline is found to be capableofquite perfectly overcoming the various recited objections and other objections that have rendered of little or no practical value the prior attempts of others. The above outline .of the present process is itself insufficient to see-ure thel best results without a more detailed description and, therefore, there will now. be recited a complete specification of a .practical process.

Assuming two-color cinematograph films are to be made by this invention, we may start with relatively reversed negatives 1.0

and 11 such as made by the method of my United States Patent No. 1,320,760, of November 4, 1919, and the final pictures 12 may be produced on ordinarystandard cinc` matograph positive film. l

First, the red-representingl negative 10 may be used to print through the carrier 14 of the print or film 12, as shown in Fig. 4, as already stated. The exposed film 12 is developed by ordinary means, such as the well known monomethylparamidophenol sulfate (metol) developer, but I prefer to use a dilute developer, without brolnid, with time limit to make the image thin and delicated. It should be a very fully exposed,

, though thin and delicate image. One minute washing should follow.' Theprint may then be immersed for two minutes in:

Solution A. C. C Water 460 Formaldehyde 8 After washing for a few minutes in water the print should be immersed in the following blue or iron toning solution:

Sol'wtofn. B.

Water 460 c. c. Oxalic acid 3.24 grams. Potassium ferricyanid 1 gram. Ferric chlorid solution, U. 16 c. c.

The print is to stay in this solution until the action is seen to be complete by examination'of the deepest shadows by reflected light at the back. Itrequires from two to live minutes, and can be carried out in white y light, though I prefer to work in a bright ing.

yellow safe light. If a more prolonged immersion is given it creates a dilliculty, namely a selective hardening of the gelatin, which action tends to spread toward the outer surface. Such hardening might impair the production of the second or red image herein. It is found to be irregular, occurring more substantially above the denser places, but it is rendered inappreciable by the useof the described .quick toning action, which alsominimizes other objections, without detriment to the color of the blue-to-green image. Immediate and thorough washing after the toning further.

minimizes any tendency to selective harden- After suoli conversion of the first silver image to a cyanotype image, and after thorough' washing, the' silver vforrocyanid base of the blue print will have its sensiv tiveness to flight restored by conversion to silver bromid. For-this purpose' the print may be immersed for thirty minutes or longer in a suitable halogen or bromine bath such as the following:

Solution C'.

-. water' 460 c. c.

Sodium clilorid 1.3 grams. Potassium bromid 4 grams. Hydrochloric acid c. c.

f The sodium chlorid and hydrochloric acid contents of this bathcan be omitted ifthe potassium bromid content is sulicientlyincreased, and fsulphuric or other acid, in smaller quantity, vcan be substituted for hydrochloric acid. It isalso desirable to greatly decrease the -light-sensitiveness of the silver bromid content of -the layer, so

4 that it approximates that of so-called gaslight paper. `This permits of carrying out the operations of drying and handling in' a very bright and comfortable yellow light,

but yet to make the prints from the green l representing negative by exposures of a small fraction of a second to a 50 )watt ni trogen lamp. This decrease of sensitiveness .is best eifected by a so-called desensitizer,

such as phenosaifranin, which maybe added to the bromid bath. To best utilize the advantages named and at the time reduce 1 Ten to Afifteen' minutes immersion in 'this bath, with occasional agitation, is sufficient. The reduction of sensitiveness by the 'action of phenosaifraninis much less than'otherwisewhen it is added to the acid bromid bath, but suicient to make its use very advantageous.

" During baths Cor CC, and subsequent operations, the ilm must be protected from actinic light.' The bath acts toconvert the lsilver ferrocyanid base of the blue print to silver bromid, thus restoring the originalsilver bromid content of the colloid layer.

previous exposure to light, and equalizes the sensitiveness of all the contained silver bromid. The print should next be thoroughly washed in .running water. It should then be dried, for example by hangingin a dry dark room. Y j Thel resenstized print may next be ex- -posed beneath the green-representing negaico -The bath further eliminates the effects of the f' tive 11, as in Fig. 6. The negative should 'be exactly registered upon the blue image.

When done visually, a green safe lightis" better and gives less diiculty than a red or orange one; but this' and other mechani'- -cal steps may performed automaticallyl by suitable appliances.

After the second lexposure follows a second development. This development should .be timed,a nd needseldom exceed one min;

ute with a normal developer. A stop 'acid can be advantageously used following the'development. Quick action of the developer, followed by the use of an acid stop bath, avoids injurious effects upon the first image. The blue image may disappear dur-v ing development but gradually redevelops 'bat-11? of water containing a .little acetic i color and .intensity in the subsequent opera,-

Potassium citrate, neutral tions of fixing and washing if Athe second May 3, 1921. Many well lknown toning and v converting processes may be used to produce the red color in the second or exterior image.

For example, I may use a copper toning process, such as suggested for the first image in said Patent No. 1,278,668 but the bath may be made up of the following:

' Solution D. Water 1000 c. c. Cupric sulfate 7 grams. Potassium citrate, neutral 28 grams.

- Solution E. Water 1000 c. c. Potassium ferricyanid 6 grams. 28 grams.

Solutions D and E should be mixed in equal parts for the toning bath. A drop of acetic acid may be advisable, as the lbath should be strictly neutral or slightly acid. A few i minutes suffices to tone the second silver image to a copper red color.

Preferably the copper red color iis strengthened or modified by dye to give the desired tone of red or red-to-yel'low, in accordance with my U. S. Patents Nos. 1,300,-

616 granted April. 15, 1919, and 1,376,940 granted May 3, 1921. The copper image 1sl capable of selectively mordanting certain dyes, available for this purpose. For example, the copper toned image after washing, may be'immersed in the following:

In this solution phenosafl'ranin equals diamidolphenylphenazonium chlorid,V and auramin equals amidotetramethyldiamidodiphenylmethane hydr'ochlorid.

In lieu of this bath it is sometimes advantageous todye irst in a red bath, and then in a yellow one until the yellow color replaces the red in the lighter shades, after which washing clears all dye out of the white parts of the picture, andafter drying the product is finished. In any case the depth of colorV should be regulated to co-ordinate with the blue image already produced,.and this is vrztatiszfactorily done by attention to the convertin strength of the dye bath, time of immersion, and amount of subsequent washing. v A quicker and cheaper method of convert ing the second color image to red consists in the. silver image to silver ferricyanid, wiich also mordants basic red and yellow dyes, and it is even practicable to accomplish this in al single combined. bath 'of potassium ferricyanid, chromic acid and certain basic dyes. For example, if, to a bath of phenosaffranin containing 1 part in 4,000' of water, is added as much of a solution of equalA parts of potassium ferricyanid and chromic acid as can be stirred into it without'gproducing much permanent precipitate, and then filtered, it will' very slowly convert the silver image to a red image, which in course of time becomes brilliant and transparent, and can be modifiedin hue by subsequent immersion in a bath of auramin. This method is particularly sensitive to the presence of any trace of the -sodium thiosulphate used in fixing the secondI silver print, which should therefore be very thoroughly washed in running water, and in the case of motion picture film, it should be wound on a frame which has never been touched by the hy o solution before immersing in the dye ath.

. A very important feature of the process ,set forth, which differentiates it from all processes heretofore proposed for producing two colored limages in a single colloid layer, both in silver bromid, by exposure and development to metallic silver, and subsequent conversion .to color images, is that in my process the second print is not limited to an uneven residual layer of silver bromid, but lis made in a fully of silver bromid, -and also 1n the presence pf an image transparent to actinic light, so that the second print can be made `upon either face of thesensitive layer,- and extend to any depth within it. It becomes possible not only to make both images in the same face and level of the colloid layer. in contradistinction to producing images (at different levels), but to make both images if desired at either the exterior face as in Fig. 8, or as in Fig. 9 the interior face, of the colloid layer, so that in the latter case the resulting compound color imagev -1s protected from abrasion on one side by the transparent carrier, and upon the other by a layer of clear gelatin. Such an image Ashould not only be many times less subject to abrasion in use than the films with images on both sides of the-carrier which are now being produced and used, but even less subject toinjury than the ordinary black-andwhite motion picture positives printed in the usual way upon the outer face of the colloid layer. I

It is worthy of note that any process depending upon the production of the second and evenly charged layer i superposed Aimage in an uneven residual layer of silver bromid has the following practical disadvantage, which is totally eliminated in my process. The residual layer 1s not only of uneven thickness, which is contrary to the normal condition for producing a photographic image with correct gradations, but it will vary in both thickness and unevenness according to the density and character of the negative used in producing the first print, and the depth to which it is developed, thus making variable and indefinite conditions for the production of the second print; and this objection can only be minimized and not removed even by saturating the colloid layer with a nonactinic dye to limit the depth of penetration of actinlc light, in accordance with my U. S. Patent '1,186,000 granted June(v 6, 1916. Only in my present process is a second print made in silver bromid under the coirect or normal conditions of exposure upon a colloid layer fully and evenly charged with sensitive silver bromid, thus securing the most favorable and definite and perfectly uniform conditions for'` the production. of a perfect image.

This application is in part a continuation of prior application Serial No. 420,431, filed October 29, 1920, the present application claiming the invention broadly, and claiming also the species in which the two images are at the same surface of the colloid layer, the other species, in which the images are at the opposite surfaces, being reserved and claimed in said copending application.

It will thus be .seen that a color photograph or motion picture film, also a method of producing it, have been described, which embody the principles and attain the objects of the present invention. Since matters of procedure, manipulation, ingredients, arrangement, combination, and other features, may be variously modified without departing from the underlying principles, it is not desired to limit the invention except in so far as specified in the appended claims.

What is claimed is:

1. In photographic color print making, the production of a silver image which is converted in part to silver ferrocyanid, followed by reconverting the silver ferrocyanid to silver bromid and then exposed to ,light under another negative andA developing a second silver print which is subsequently converted into a color print. v

2. The production of a silver image in a gelatin silver bromid layer, followed by converting the silver image to a color image by aprocess producing silver. ferrocyanid, followed by converting the silver -ferrocyanid to silver bromid, thus restorin substantially the original silver bromi content to the gelatin layer, followed by exposing to light under another negative and i ing the silver image to a color image by a process producing silver ferrocyanid, followed by converting the silver ferrocyanid to light-sensitive silver bromid, thus substantially restoring the original evenly dis\y tributed light-sensitve silver bromid content of the gelatin layer, followed by exposing to light under another negative and developing a silver print which is subsequently converted to another color.

4 lThe production of a color image in a. gelatin silver bromid layer, followed by the production of a silver image in -the same layer which is not limited to an uneven residual layer of silver bromid left after the production of the first image, but is produced in a layer fully and evenly charged with light-sensitive silver bromid.

5. In the successive production of two different color images in a gelatin silver bromid layer, rendering the base of the first 1 image unredevelopable without subsequent exposure to light, byreconverting it to light sensitive material, in contradistinction todissolving it out or making it inert lto light and development.

6. As an intermediate product in a color photography process, a gelatin silver brolmid film contammg a color image, but

evenly charged Ithroughout its body with light-sensitive silver bromid.

7. As an intermediate product in color photography process, a gelatin silver bromid film containing a color image, but evenly charged throughout its body with vevenly light-sensitive silver bromid.

8. As an intermediate product in a co-lor photography process, a gelatin silver bromid lm containing a color image which is transparent to actinic light, -but which film A is also' evenly charged' throughout body With light-sensitive silver bromid, and thus adapted'to the production of a second image py exposure and development upon either ace.

9. As an intermediate product in a color photography process, a gelatin silver bromid' film containing a color image which is transparent to actinic light, but which film is -also evenly charged throughout its body with light-sensitive silver bromid, and thus adapted'to the production ofasecond image byl exposure and development upon either face, and without limitation to an uneven 125 residual layer of silver bromid left after the production of the first image.v

10. As an intermediate product in a color photography process, a gelatin silver bromid film containing a color image which is transparent to actinic light, but which is y also evenly charged throughout its body with light-sensitive silver-bromid, and thus adaptedfto the production of a second image by exposure and development upon either face, and to any desired depth within the layer.

11. The production of a silver image in a gelatin silver bromid layer, followed by con- Verting the silver image to a color image by a process producing silver ferrocyanid and a color transparent to actinic light, followed by converting the silver ferrocyanid to lightsensitive silver-bromid, thus substantially restoring the original evenly distributed lightsensitive silver bromid content of the gelatin layer, followed by exposure to light under another negative and upon the same face as the first print, and developing a silver print which is subsequently converted to another color, and which therefore occupies the same face and level as the iirst print.

12. Two dierent color images produce-d successively in the same colloid layer, each by exposure and development of silver bromid followed by color conversion, and both in the same face and level of the colloid layer.

y 13. Two different colored registered and blended images buried in a single colloid layer, protected on one side by the transparent carrier and upon the other side by a covering which is part ofthe original colloid layer.

14. Method of producing a color photograph or film by blending differently colored images within the same colloid layer containing a silver haloid upon a suitable carrier consisting in making each of saidr-espective images by the action of light upon a silver haloid followed by development and conversion to color images, the first image being color-converted from the silver image by a process producing a ferrocyanid compound, and such compound being thereafter submitted to the action of a halogen to resensitize the colloid layer before exposure for the second image. e

l5. Method of producing a color photograph or lilm consisting in making an image by exposure of a layer sensitizedwith silver bromid, developing such image, colortoning such image by a process producing silver' ferrocyanid, treating the same to reconvert the silver salt to silver bromid, thus restoring sensitiveness, making a second image by exposure of the same layer, and developing and color-toning the second image.

16. In the process of producing two images in a single layer of colloid emulsion 1containing a silver haloid by successive printings with intermediate development and conversion of the first image, restoring the evenness of sensitivity after the development andconversion of the first image by recouvert-ing to sensitiveness the silver used in the first image, so that the second image can be exposed and developed from a uniform emulsion to yield normal gradations.

17. In the production of color prints in a single colloid layer containing a silver haloid on a transparent carrier, printing a silver image from a red record negative through the carrier, developing it as a silver image adjacent to the cari'ier, convert-ing single colloid layercontaining a silver haloid' on a transparent carrier, photographically producing a silver image from a red record negative and converting itl to a pigment blue-to-green print by chemical treat-ment without dyeing, conjointly with treatment with a. haloid, and the subsequent production of a red image in the same colloid layer.

19. In the production of photographic multi-color prints in a single colloid layer containing a silver haloid, the production of a silver image from a red record negative followed by conversion to a pigment blueto-green print by chemical treatment without dyeing, and conjoint treatment with a haloid to prevent redevelopment ofthe original image together with another image subsequently produced in the same colloid layer. In testimony whereof, I have aiixed my signature hereto.

FREDERIC E. IVES.

Images