US 3579338 A
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May 18, 1971 s mgo-oou EI'AL 3,579,338
I PROCESS FOR MAKING METAL-GLOSSY IMAGES AND PROJECTION USING THE SAME Filed Feb. 14, 1968 INVENTORS SHINGO OOUE HIROYUKI UEDA YOSHIHIDE HAYAKAWA ATTORNEY 5' United States Patent Int. Cl. G03c 5/26, 5/2 4; G03b 27/54, 27/76 US. Cl. 96-50 Claims ABSTRACT OF THE DISCLOSURE A projection process which comprises subjecting a silver halide image to a sulfiding treatment, treating the image thus treated with a solution containing a solvent for silver halide to provide a metal-glossy image, applying to the surface of the metal-glossy image an illuminating light beam for transmission and an illuminating light beam for reflection, combining the penetrating light beam and the reflected light beam, and projecting on a screen the combined light beam to provide a projected image having various contrasts. A process for making a metal-glossy image which comprises subjecting a silver halide image to a sulfiding treatment and then treating the image thus treated with a solution containing a solvent for silver halide.
BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates to a process for making a metal-glossy image from an image composed of silver halide. It also relates to an image projection process which comprises providing illuminating light for-transmission and illuminating light for reflection to the metal-glossy image while varying the light intensity ratio, combining the transmitted light and the reflected light and projecting the combined light on a screen to obtain projected images varying in contrast from the nunal image.
(2) Description of the prior art In some cases where a photographic image of a negative film is printed on a printing paper or positive film for cinema, a duplicating negative film is obtained from a positive film by printing or a slide or cinema is projected, it is often desired to vary the contrast of an image so as to give a suitable tone reproduction or to give a better representation within a specified region of density. In a developing treatment, for example, an image having too high a contrast is obtained where the treatment is too long while an image having too low a contrast is obtained where the treatment is too short. If a metal-glossy photographic image can readily be made having a high reflectance at an image area of high transmission density so that the contrast of the image may be varied easily by means of a contrast variable printing apparatus, an automatic printing of a printing paper, printing of a movie film, etc., many advantages are thereby obtained. The reason is that, in an automatic printing machine using a roll paper, it is impossible to exchange a printing paper for another according to the contrast of an image. Accordingly, the quality of an image obtained by an automatic printing machine will be markedly improved if the contrast of an image could be freely varied by an optical system of a printing machine. The same is true in printing of a positive film for cinema.
Up to the present time, to this end, there have been proposed a contrast variable enlarger using a flying spot tube, a printer and an inversion viewer with a television system, a printer and an inversion viewer utilizing quench- Patented May 18, 1971 ing phenomenon exhibited by fluorescent materials. However, these devices have such disadvantags that the structure is complex, the production cost is high, a rather dark image is obtained for practical use as an enlarger, and the sharpness of the image is lowered.
It is an object of the invention to provide a process for making a metal-glossy image from a silver halide image wherein the reflectance at an image area of high transmission density is higher than that at another image area of low transmission density.
It is another object of the invention to provide an image projection process for obtaining projected images varying in contrast by the use of such metal-glossy image.
SUMMARY OF THE INVENTION More specifically, the process consists in subjecting an image composed of silver halide to a sulfiding treatment and treating with a developing solution containing a solvent for the silver halide, and the latter image projection process consists in giving illuminating light for transmission and for reflection to the surface of the metal-glossy image obtained by the former process while varying the light quantity ratio, synthesizing the transmitted light and reflected light and projecting on a screen to obtain projected images varying in contrast.
A photographic image having an optional contrast can be made by printing an image obtained by the image projection process of the invention on a suitable light-sensitive material.
The metal-glossy image of the invention has a higher reflectance as a mirror surface at a high transmission density area than at a low transmission density area, and can readily be made.
Furthermore, it is possible to vary the contrast of an image or to reverse the same by giving simultaneonslv transmission illumination and reflection illumination to the metal-glossy image to cause image formations respectively and varying relatively the intensity of light of the transmission illumination and the intensity of light of the reflection illumination, whereby projected image having high brightness can be given on a screen.
In the metal-glossy image of the invention, not only can the contrast of an image be varied within a certain range by the foregoing optical system, but also, if reflection illumination is given to an image, such as forming a negative image through transmission illumination, a positive image is obtained. That is to say, the positive-positive photographic process can be carried out according to the invention as in the case of subjecting a photographic lightsensitive material to reversal developing, since a negative image is projected, printed or viewed as a positive image, and vice-versa. Moreover, the metal-glossy image of the invention is available for the reversal viewer, projection of a slide or movie, etc.
DETAILED DESCRIPTION OF THE INVENTION The process for making the metal-glossy image of the invention will now be illustrated in detail.
The image having a metallic gloss according to the invention is obtained, treating an image composed of silver halide with a solution containing a sulfiding compound to form fine particles of silver sulfide having a size of from 0.001 to 0.1 micron in said silver halide image and then developing with a developing solution containing a solvent for silver halide and a silver salt. In this procedure, the so-called fatigue solution in which a suitable quantity of silver halide sensitive material was immersed may be used in place of the developing solution containing a silver salt.
Preparation of the image composed of silver halide will become apparent from the following illustration relating to one of many known methods.
Referring to FIG. 1, one embodiment of the optical system is illustrated wherein a photographic image made by the photographic process of the invention is projected on a screen 'while varying the contrast thereof. In an optical system wherein image 1 is projected on light-sensitive material for printing or screen 3 through projection lens 2, image 1 is subjected to transmission illumination by means of light source 4 for transmision illumination and condenser lens 5 for transmission illumination, while being subjected to reflection illumination by means of light source 6 for reflection illumination, condenser lens system 7 for reflection illumination and half silevered mirror 8 (or partially reflecting and partially transmitting mirror). Both of the illuminating systems are so designed that the illumination intensity ratio may be varied, for example, by inserting light quantity modulators 9, 10 in the illuminating systems respectively or by making the intensity of the light sources variable. The light modulator is so composed that two optical wedges are moved in the reverse direction to each other or two sheets of polarizers are so arranged, the mutual azimuth of which is variable. In a case where incandescent lamps are used as light sources 4, 6 and the voltages are varied to control the quantity of light, the colors of the penetrating illumination and reflecting illumination become different. If it is necessary to balance the color in such a case, a monochromatic filter is preferably used for the projection optical system.
It will now be illustrated how the contrast of a projected image from the synthesis of the transmitted light and reflected light of an image is varied.
If E is the intensity of illumination of a transmission illumination of a reflection illumination light on the same illumination of areflection illumination light on the some image, T is the transmittance of the image to an incident ray and R is the reflection factor, the brightness B of an projected image is given by the following relation:
B=C(E T+E R) where C is a constant determined by F-number of a projection lens, constants of the optical elements and their arrangement. In the case of E =0, that is, utilizing only a penetrating light, B is proportional to T, for example, an ordinarily developed negative gives a negative image. In the case of E =0, that is, utilizing only a reflecting light, B is proportional to R, for example, an ordinarily developed negative gives a reversed, positive image. By selecting suitably the ratio of E an B a desired contrast from negative to positive can be given. By taking gamma as a value representative of the contrast and as a value representative of the ratio of E and E the change of gamma with K is as shown in the following table, for example withrespect to the image obtained by the procedure of the example. In the table, the gamma of negative character is plus and that of positive character is minus.
K: Gamma 0.00 -1.0 0.27 0.5
The advantages or effects of the photographic image having a metallic gloss according to the invention are summarized below.
(1) A positive image having a desirable tone can readily be made from any of various photographic images having a metallic gloss and contrast of a wide range as a matter to be photographed by the use of a positive film or printing paper having one kind of contrast.
Since it is possible to view a negative image as a positive image through reversing, the planning of a picture is possible prior to printing on a printing paper.
(3) Since, if a penetrating illumination or reflecting illumination is effected on a specified area of an image alone, the contrast of the area only is varied, the contrast of an image can be made uniform throughout a picture by adjusting to that of another area in the picture.
The following example is given in order to illustrate the invention without limiting the same.
EXAMPLE Procedures for making the metal-glossy image of the invention are exemplified in the following. The steps from (1) to (7) are by known processes for making a photographic image composed of silver halide and those of from (8) to (13) are by the process of the invention.
(1) Exposure: A silver halide photographic sensitive material is exposed in a camera or printed with another photographic image.
(2) Developing is carried out at 20 C. for five minutes using a developing solution of the following composition:
Water (50 C.)-750 ml. Monomethyl-p-aminophenol-1 g. Anhydrous sodium sulfiteg. Hydroquinone9 g.
Sodium carbonate monohydrate-29 g. Potassium bromide6 g.
Water to 1000 ml.
(3) Water washing: 20 C., 1 min. (flowing). (4) Fixing is carried out at 20 C. for three minutes using a fixing solution of the following composition:
Solution I- Water (50 C.)-600 ml. Sodium thiosulfate300' g. Solution II- Water (50 C.)-200 ml. Anhydrous sodium thiosulfate-15 g. Glacial acetic acid-12 ml.
Solutions I and II are prepared separately, cooled at room temperature and Solution II is added to Solution I little by little, with stirring, so that the total volume is 1000 ml.
(5) Water washing at 20 C. for five minutes (flowing).
(6) Bleaching (halogenizing) is carried out at 20 C. for three minutes using a bleaching solution of the following composition:
Potassium bichromate-ZO g. Hydrochloric acid (30% )-50 ml. Water to 1000 ml.
-It is preferred to use a bleaching solution which forms silver chloride.
(7) Cleaning bath: Immersing in 5% NaCl solution at 20 C. for two minutes. This procedure may be omitted, but should be carried out if possible in order to obtain a good result.
(8) Swelling: Irnmersing in water at 60 C. for four minutes to swell the emulsion layer.
(9) Squeezing: Water on the emulsion layer is wiped off.
(10) Forming silver sulfide: -In a closed vessel, an aqueous solution of potassium sulfide of mol/l. is mixed with sulfuric acid of rnol/l. to generate hydrogen sulfide, and the photographic sensitive material processed by the foregoing steps 1 to 9 is allowed to stand therein for ten minutes. The silver halide layer is exposed to hydrogen sulfide and particles of silver sulfide are formed therein.
(11) Metal-glossy developing is carried out at 30 C. for four minutes using a developing solution of the following composition to obtain a metal-glossy image:
Water-600 ml. 1-phenyl-3-pyrazolidone-1.7 g. Anhydrous sodium sulfite-60 g. Hydroquinone-ZO g.
Anhydrous sodium thiosulfate60 g. Boric acid2.7 g.
Sodium carbonate monohydrate47.5 g. Potassium bromide-5.7 g.
Water to 10000 ml.
The following materials are added thereto:
Aqueous silver nitrate solution )-100 ml. Potassium bromide100 g.
Although silver nitrate gives a better result, it is not necessarily required.
(12) Water washing: 30 seconds, flowing.
(13) Drying: About 15 minutes, hot air.
An image having a metallic gloss is obtained by the foregoing steps. Step 9, squeezing, may be replaced by immersion in a surfactant solution. The metallic gloss appears after the layer is dried.
In order to examine the degree of gloss of the metal glossy image thus resulting, the surface area having maximum metallic gloss is illuminated at an angle of incidence of 45 and the reflected rays are measured in the normal direction of reflection having an angle of 45 in the plane of incidence against a line vertical to the surface. The measured value is 30 in this case, and 100 in the case of a vacuum vapor deposition surface of aluminum. The larger this value, the greater is the metallic gloss. When a metal-glossy image has such a degree of gloss, the contrast of the image can be sufliciently varied or a reversal image can be formed by changing the ratio of intensities of the reflecting illumination and transmitting illumination, as shown in Table 1.
In the process for obtaining a metal-glossy image in accordance with the invention, the sulfiding treatment may be carried out by immersing a sensitive material in an aqueous solution of hydrogen sulfide as well as a dilute solution of an inorganic sulfide, such as sodium sulfide or ammonium sulfide and an aqueous solution of an organic compound including unstable sulfur atoms, such as, thiourea, its derivatives or thioacetarnide, in addition to the exposure to hydrogen sulfide gas as mentioned above.
The solvent of silver halide to be added to a developing solution for glossing as in the example is selected from the class consisting of thiosulfate, sulfite and halogen salts besides the well known solvents, such as, thiocyanate, ammonium salts, organic bases, etc.
Methods of making images composed of silver halide are classified roughly into the following three groups, in addition to the method of converting into a silver halide image by subjecting a silver image to bleaching, said silver image being obtained by developing and fixing a silver halide photographic light sensitive material after exposure:
(1) The first is a method of utilizing the so-called photoetching art. This comprises providing a layer of light sensitive polymer the properties of which change with light on a layer of silver halide coated onto a support, adhering thereto a photographic image formed on a film, exposing the assembly to a light existing in the sensitive Wavelength region of said polymer, treating to form an image of the light sensitive polymer according to said photographic image, treating 'with a solvent for silver halide to remove silver halide at an area where the polymer is removed, and then removing the polymer layer to retain a photographic image composed of silver halide.
(2) The second is an application of the printing method. That is, a printing plate of an image is made by the conventional method and printed on a support, such as, paper or film, by the use of a solution containing silver halide and having a suitable viscosity as Well as adhesiveness to the support in place of a printing ink, thereby to give an image composed of silver halide. In some cases, a silver halide image may be made by carrying out printing on a layer of silver halide according to an image by the use of a solvent for silver halide in place of a printing ink and treating with water to remove silver halide partly.
(3) The third is a method of obtaining a silver halide image comprising writing an image directly on a support, such as, paper or film, in pen or brush by the use of a solution containing silver halide. In some cases, a silver halide image may be obtained by writing an image directly on a light sensitive material of silver halide in pen or brush by the use of a solvent for silver halide in place of an ink to remove silver halide partly.
The process of the invention is applicable to any of the images composed of silver halide made by the foregoing methods, resulting in an image having a metallic gloss in each case.
In a case where a paper or white film base is used as a support and a metal-glossy image is formed thereon, the image is not necessarily suitable for projection with change of the contrast due to a high penetrating density and low reflecting density of said support, but finds uses for the publication of advertisements, displays, etc., being capable of forming a peculiar visual effect due to the metallic gloss.
What is claimed is:
1. A process for making a metal-glossy image which comprises subjecting a silver halide image formed on a support to a sulfiding treatment and then treating the image thus treated with a solution containing a solvent for silver halide.
2. The process as claimed in claim 1 wherein said silver halide image is formed by halogenizing a silver image of a photographic silver halide light sensitive element with a bleaching solution which forms silver halide.
3. The process as claimed in claim 1 wherein said silver halide image is a silver chloride image.
4. The process as claimed in claim 1 wherein said sulfiding treatment is conducted by treating the silver halide image with a hydrogen sulfide gas.
5. The process as claimed in claim 1 wherein said sulfiding treatment is conducted by immersing in an aqueous solution of hydrogen sulfide.
6. The process as claimed in claim 1 wherein said sulfiding treatment is conducted by immersing the silver halide image in an aqueous solution of a sulfur compound.
7. The process as claimed in claim 6 wherein said sulfur compound is selected from sodium sulfide, ammonium sulfide, thiourea, a thiourea derivative, and thioacetamide.
8. The process as claimed in claim 1 wherein said solvent for silver halide is an aqueous solution of a member selected from the group consisting of a thiosulfate, a sulfite, a halide, a thiocyanate, an ammonium salt, and an organic base.
9. In a projection process which comprises applying to the surface of an image-containing element an illuminating light beam, applying to the opposite surface of said imagecontaining element a second illuminating light beam, combining the light beam passing through the image-contain ing element and the light beam reflected from the imagecontaining element to form a combined light beam and projecting on a screen the combined light beam to provide a projected image having various contrasts, the improvement which comprises using as the image-containing element the metal-glossy image prepared according to the 11. The process as claimed in claim 1 wherein said silver halide image is formed by preparing an assembly comprising a support having a silver halide layer coated thereon, a light sensitive polymer layer coated on said silver halide layer, and a photographic image on said polymer layer, exposing said assembly to light of a wave length to which said polymer layer is sensitive, removing a portion of said polymer layer to form an image in the polymer layer corresponding to the photographic image, treating said assembly with a solvent for said silver halide to remove said silver halide from said silver halide element at the polymer removed areas, and removing said polymer layer.
12. The process as claimed in claim 1 wherein said silver halide image is formed by printing a silver halide image on a support using a solution of a silver halide.
13. The process as claimed in claim 1 wherein said silver halide image is formed by printing on a support having coated thereon a silver halide layer using a solvent for the silver halide in said layer.
14. The process as claimed in claim l wherein said silver halide image is formed by writing on a support using a solution of silver halide.
15. The process as claimed in claim 1 wherein said silver halide image is formed by writing on a support having coated thereon a silver halide layer with a solvent for the silver halide in said layer.
References Cited UNITED STATES PATENTS 3,149,970 9/1964 Weyde 9-648 2,783,678 3/ 1957 Andreas et al. 355-70 3,475,096 10/1969 Ooue et al. 355-70 NORMAN G. TORCHI-N, Primary Examiner E. C. KIMLIN, Assistant Examiner U.S. Cl. X.R.