DE369403C - Process for different coloring of separate images in a colloid carrier - Google Patents

Description

GERMAN EMPIRE

ISSUED
FEBRUARY 19, 1923

REICH LATE OFFICE

PATENT LETTERING

- M 369403 CLASS 57b GROUP-18

(K-jgoio VI \ 5jl ·)

William van Doren Kelley in New Jersey, V. StA.

Method for differently coloring separate images in a colloidal support. Patented in the German Empire on September 3, 1921.

According to the Union Treaty of June 2nd, igii has priority for this registration of the application in the United States of America dated May 24, 1920.

The invention relates to, and particularly relates to, photographic image processing a process and product whereby transparent layers for the subtractive how can be generated for the additive process that serve for the reproduction of natural color images or

Create a grid with only a single layer on one side of a clear one Use carrier.

Although various methods of producing subtractive color images are described and patented using two or more different color values

Images on the same side of the same transparent support showed and assumed that the layer was made sensitive for each subsequent print by a new coating (ropes, American patent 654766) or that the silver of the layer for a print and the bichromate treatment of the Using gelatine for a second print (C ο χ, British ίο patent 15648/1914) or re-sensitizing the gelatine with iron (I ν es, American patent 1278668), no commercially viable method of exploiting these routes has yet been developed. It has also been proposed (Fox, American patent 1,166,123), ^em picture ^m to copy the layer it a part of developing this and tone to print the second image in the optionally present residue of the sensitive silver to develop and Bleach decolorization of the first image when developing the second, then colorize the second image, and then restore the color of the first image. This method is unsatisfactory because it shows no way of preventing the post-development of silver when the second image is copied due to the presence of developable silver compounds such as silver ferrocyanide, which causes the final image to be unsatisfactory in detail. This method is also unsafe as a result because of the difficulty in maintaining sufficient sensitivity for the second print, while the restoration of the discolored first image is not always accurate in color reproduction, so that it often has to be modified later by further tone or post-inking treatments; furthermore, even the second image may have to be modified in color to compensate for it. Further, the bleach baths that are applied out for this \ ^r, only basic colors suitable to be dealt with severely businesslike because they are dichroic, ie, because they result in different densities of different colors. The methods which start from resensitizing the gelatin, e.g. B. by means of bichromate, and use a printing positive and use the Pinatypie method for dyeing or sensitize with iron and use a negative for printing, are not perfect because of the slowness and the many more numerous work steps required. It is also proposed to combine a copper-toned picture with basic colors in order to improve the red that can be obtained from basic colors alone (I ν es, American

Patent 1300616), but overcomes this procedure not even the restrictions that are based on the basic colors when combined with a complementary colored image, it results in the required one Review of the finished film.

The above-mentioned references mostly raise the requirement that an exact congruence of the two images should be ensured, but neither states how this should be done for a commercially deliverable amount of colored motion picture film can be achieved can, and yet no successful result can be obtained without exact registration of the two images over a long strip will.

Even if a process that uses a single-layer positive film, this Layer the various complementary images bears an initial advantage over procedures who use a double layer film because of the cost of the However, this initial advantage can easily be lost if not the subsequent ones Working stages allow the use of ordinary negatives, simple and quick to execute and adaptable enough to adapt to fluctuations, large-scale work with objects picked up under various conditions is unavoidable cling.

According to the invention, the sensitive silver originally present is generally used This secured the layer used for both images by adding a good second print that the original emulsion is temporarily replaced by an easily exchangeable one Dye is made less sensitive that washed out during the first development and a significant residue of sensitive emulsion for the second print leaves behind. The first picture that z. B. copied and developed through the back of the carrier, but is not fixed, it is bleached in such a way that it is capable of absorbing paint, the special property of which is bleach developing unexposed silver or the silver in the bleached image ito to prevent during the second print. After the second picture from the front has been copied, both are fixed in sodium thiosulfate, and the first, which is still for acidic or azo colors is receptive, z. B. be tinted orange-red, while the second z. B. is toned blue-green with iron ferrocyanide or bleached and colored blue-green will. This method gives a subtractive two-color image based on the American one Patent 1259411, but in a single layer, with the images through the

369408

Mitfei and procedure described below are brought to congruence. ■

For an additive transparency based on the American patent 1337775 have been the halftone prints shown in Fig. Ι of the patent mentioned are shown, one from the rear and the other from the front, made separately, namely in front of or ίο immediately after copying from the negative, so that each grid part and the image sections in between are identical Color in complementary colors. The creation of the cover · for the grid5 printing is carried out using the pen means, which is explained in more detail with reference to Fig. 7 below, but is not the subject of the invention. One modification of this basic procedure is this Applying grid lines that cross each other, eliminating the need for a Exact congruence of the lines of one grid with the gaps of the other is not necessary; It has been shown that the black points at the line crossings are not in the Make image projection noticeable in a disturbing way, nor reduce the brightness, nor the Affect color.

In the drawings is: I.

Fig. Ι a section through the new positive film to be colored,

Fig. 2 a section after printing and developing the first image,

Fig. 3 is the same section after the first image has been faded and developed of the second picture,

Fig. 4 is a section showing the first picture in ■ one color, e.g. B. red, colored shows and the second toned, z. B. blue-green.

Fig. 5 is a section similar to that of Fig. 2 for additive transparency. !

Fig. 6 is a section similar to that

Fig. 3, wherein the first image and raster \ bleached pattern and the second image and the I

matching grids for toning |

is done. . \

Fig. 7 is a modification with each other; intersecting grid lines. !

Fig. 8 is a section according to Fig. 7, |

Fig. 9 is a section showing the crossing of the lines in two on the support each other opposite layers shows.

Fig. 10 shows a red value negative in the usual way,

Fig. 11 a complementary green value negative.

Fig. 12 shows the finished positive of Figs. 7 and 9, and

Fig. 13 illustrates a section of a delicate grid support, e.g. B. a negative, according to the invention.

According to the invention, a single, j photosensitive substance such as silver salt, carrying layer subjected to two exposures with an intermediate treatment after the first exposure of such a nature that no redevelopment or ^{post-development.} Occurs during the second exposure · The two exposures may in the mutually opposite parts of the layer are made by effecting one through the back of a transparent support, and the other on the layer side an additive two-color see-through image based on the inventor's American patent 1337775 can also be produced in one layer by printing from opposite sides. The two prints can also be done next to each other in order to fulfill the same additive principle, λνΐε ζ. B. in the case that a finely divided additive grid is provided to produce a single negative of two or more colors. In all of these different possibilities, success is achieved in that the method is guided in such a way that the first image cannot be influenced when the second image is copied, after the first has already been treated. By overcoming this difficulty, it is possible to obtain transparencies from a single layer emulsion with considerable savings in fabric, cost, and labor over previous double-layer positive or re-layered processes.

A positive emulsion layer is used for the production of a subtractive transparent image, which is treated with an easily washable dye, such as tartrazine, which has the effect of preventing the passage of light to slow down through the emulsion so that still a substantial part of Light sensitivity remains on the side facing away from the incidence of light for the second print. This dye is washed out during the first development and it is immaterial whether the first print of. the layer side or the rear side; however, it is practically preferred to print the first print through the transparent back gain weight. A carrier of the type described here is shown in FigDi. Its application, is, as far as could be ascertained, new in color photography and is becoming ever so Prove as a decided advance by making the application people more ordinary technical dexterity that are now able to produce color value negatives produce, but are only able to obtain the substances with great difficulty, those necessary to carry out the relatively complex and expensive procedures

are as previously suggested. This new product can be factory-made in large quantities and be marketed just as easily as the current commercial plates or films. The next step is to copy the first image in the layer through the back, as shown in Fig. 2, and develop and wash it out, removing the easily washable dye and any developer residue. Thereafter, the gelatin, e.g. B. by immersion for ten minutes in a ten percent formalin solution, hardened and then the silver bleached in a solution which has the special property of preventing the post-development or redevelopment of reduced silver during the second copying.
A satisfactory bleach bath is:

Water 1 000 ecm,

Sodium dichromate. ". 2.235 S> chromium ammonium alum 2.932 g,

Copper sulfate 12.468 g,

Sulfuric acid 0.083 g,

Potassium bromide i7> ⁸ 35 S '>

however, other baths can also be used or the \ ^? conditions are changed. Apparently a bromocopper image is formed in the layer immediately next to the developed black silver, which fixes acidic or azo dyes without being influenced by the fixing bath or by certain clay baths or by gelatin dyeing baths or by the second development.

The first image is now see-through and in

Striking light is barely visible, and there is still enough sensitive residue Silver available for a second print. In the case of mass production, the exposure time can for the second print can be shortened by reducing the photosensitivity by a five minute Bath of the following composition is increased:

Chromic acid 6.25 g,

Potassium bromide 12.5 g,

Water 1,000 ecm.

The film is then washed and dried and is now ready for the application of the second copy, which is made in register with the first and then developed in a developer, such as Pyro, which does not affect the first bleached image. As ER is clearly ι, the first image is not fixed correctly with hypo. After the second print has been made in the washed and dried, photosensitive layer, the entire film is fixed in sodium thiosulphate, washed and preferably dried. He is now. in the condition of Fig. 3, the bleached image being in a second layer and the developed black image in the other or in different parts of the same layer.

The film is now in a mixture of red and orange, acidic or azo colors colored to give the desired red value, with colors such as. B. Phloxin and Orange Y are suitable for red coloring. The bleached image to be colored is an image complementary to the inking color, in this case being of a green-blue Is copied negatively. If the bleached image is to be colored green or green-blue, it becomes negative from a red value printed; for coloring is then a color,. like patent blue, suitable.

If the second copy is made from a red value negative, it can be tinted slightly blue-green, e.g. B. by a blue iron ' procedure. Should the hue be red in cases where the bleached image is colored blue-green different red-clay baths are known, such as uranium, copper, etc., which cannot be described in detail here need, as they are in works like Cassel's Cyclopedia of Photography and andego other reference works. One final wash completed after toning the movie. After dyeing, ordinary washing should bring the color out of the lights completely, but can in some cases the wash water may be slightly acidified with acetic acid.

In Fig. 1 to 4, 1 means the transparent one Base, 2 the layer, 3 the first to be bleached and colored, and 4 the second image to be toned.

According to Figs. 5 and 6, a grid pattern is made in each level of the positive with the Image copied and colored in the same color as in the American patent 1337775, whereby the grids are offset so that a clear part of a sample part facing the other. Lines, squares, and other geometric patterns can be used, as long as only the clear ones Parts correspond perfectly to the sample parts. In Fig. 5, the lines are through 5 and the gaps indicated by 6 in the inner surface, and in fig. 6 the gaps are indicated by 7 and denoted by 8 the lines or other patterns.

To avoid the difficulty of matching the gaps of a halftone print with the To bring grid parts of the other to coincide, the one illustrated in Fig. 7 is expedient Arrangement, according to which a grid of parallel lines and gaps for

the pressure and the same grid of lines and spaces may be cross erwendet to the other pressure \ ^r. In such cases, the crossing points of the lines produce black fields that have no effect in the additive color generation; the clear parts show white, where white must appear, and black, depending on the proportions, for black or red or green, while the

ίο Parts of the line pattern between the crossings in the white areas of the picture show red and blue-green respectively, and in other parts of the picture these give small parts of red and blue-green according to the color to be reproduced additively white.

In Fig. 8 is a section of Fig. 7 is shown, with the grid lines intersecting ^{at 90 0;} 9 is the inner pattern and 10 is the outer. In Fig. 9, a carrier 1 provided with two layers carries these grids 9 and 10, which belong to one another, on different sides. In Fig. 10 a red screen negative is shown in the usual representation and in Fig. 11 a green screen negative, while Fig. 12, as far as the limits drawn by the graphic reproduction allow, this by superimposing the prints after the negatives of Figs. 10 and 11 generated see-through image illustrated. In Fig. 12, the section W shows white by the additive effect of the white part 11, the red parts 12 and the green parts 13, while the black parts 14 formed by the crossing points are ineffective. The red section R is formed from the parallel red bands which form a continuation of the particles 12 and are separated by black bands 15. The black parts B are all black due to the combined subtractive effect of the color lines and images. The green section G is produced by the green bands which form a continuous stringing together of the parts 13 ″ and are separated by black bands i6 _; similar to the bands 15, but at right angles to them.

In Fig. 13, the carrier 1 is with a Layer 17 provided on one side, and on

So the opposite or on the one on the same side there is another part that is to be printed with a raster image, the parts 18 being bleached and dyed red and the parts 19 in between to be tinted green to such a color screen to obtain, through which the layer 17 can be exposed to an additive color value drawing to obtain. At first it can be an ordinary picture carrier with the screen and then made sensitive to exposure, either j on the same or on the opposite

lying side, or the screen part can be made and colored in front of the picture part. This makes for a simpler method of making a grid plate or film than that was previously possible. As far as is known, earlier efforts in this direction have failed at the difficulty of two colors side by side in the same layer in separated Get printing without the first image post-developing when printing the second became. This difficulty is eliminated by the method described above, so the invention is not limited to a method of taking different images rather, to produce the same photosensitive layer in different planes can be used in the same way to generate different images side by side, with each one its color by coloring and the other most appropriately chemical toning.

One or both images can, instead of voh to be copied from a negative and colored in the places of the developed silver made a positive, then developed and bleached with the above be treated, which tans the gelatin in the place of the silver precipitate, go so that it repels certain colors, whereupon the untanned gelatin to form the Is colored positively, e.g. B. with acid green L for blue green and Ponceau 3 R B, Creosine for red or red-orange. In these processes, the hardening stage is omitted. Once one picture has been produced in this way, the other can be toned as described above or colored.

Among the various possible modifications to the invention, one can be seen important feature the application of such a bleaching agent before the eventual No silver compounds developable again by the second exposure results, such as silver ferrocyanide or other compounds that are more or less sensitive to light and by different previously known bleaching agents were produced, e.g. B. by that after the American one Patent 1273457 by C a ρ s t a f f.

An important feature is that the two print images are printed in register will; this is achieved, as shown in Fig. 7, in that the usual elongated Find film perforations for bringing about the cover use. A hole in the negative is preferably chosen, and a fully fitting pin 20 is pushed through this and, if necessary, is pushed through a straight opposite opening brought a cooperating pin 21.

which fits into the perforation from top to bottom, but the hole does not go in the vertical direction to fill in.

Everything opposite shrinkage of negative and positive is then on one side on that fully matching pin 20 (Fig. 7) added *. The development and drying of the Positive after the first print and before the second print causes little shrinkage. But because of the fact that a corresponding perforation is made when the second print is produced of the negative and the same positive hole as well as a fully fitting pen for the induction the overlap is used as long as the second image remains in practically identical relation to the first, results from the shrinkage no difficulty whatsoever. Whether copied on the same side of the positive will or on the opposite side, in either case will be the same hole in the positive used for the full mating cover pin 20, and if a second pin 21 is used for this the same positive hole is needed for this pin in both cases.

In addition to moving images, the invention is also applicable with suitable modifications applicable to all other types of work including plates and paper and also for. Stereoscopic images.

Claims (7)

Patent Claims: i. Method of differently coloring separate images in a colloid support, characterized in that it contains a bleached, color-receiving image ' and a different, reduced silver picture is created in such a way that that in the layer initially a silver image ί is created, that the layer then without ' Fixing hardened and then treated with a bleach, whereupon in ι the silver residue is created by a new exposure, a second image, and that after fixing has been carried out, the first image is colored and the second is toned in a different color. • 2. The method according to claim 1, characterized in that a bleaching agent is used that the first silver image in a compound transferred by the second exposure and development failed is influenced, but the image areas of this first image are receptive to acidic or azo colors, after which the second image is copied and converted into an image of reduced silver is developed. 3. The method according to claim 1 and 2, characterized in that the first Image from the back, the second from the front of the single-layer image carrier is printed. 4. The method according to claim 1 or the subclaims, characterized in that that after developing and bleaching the first image, the layer with one of the sensitivity of the still photosensitive Residue. increasing solution, preferably from potassium bromide and chromic acid, is treated. 5. The method according to claim 1 or the subclaims, characterized in that that the photosensitive layer should be cleaned with an easily washable, light retardants, such as tartrazine, which causes that in the first exposure a sufficient residue of sensitive silver remains in the layer and through the Development of the first image is removed. 6. The method according to claim 1 or the subclaims, characterized in that that after the first image has been developed, a bleach bath containing copper and chromium is used. 7. The method according to claim 6, characterized by the application of a Bleaching bath, the following ingredients per 1,000 ecm of water, preferably in the specified quantities, contains: Sodium dichromate 2.24 g, Chromammonium alum ... 2.4 * g, Copper sulfate 12.5 g, Sulfuric acid ο, ΐοο g, Potassium bromide 17.8 g. For this purpose ι sheet of drawings.