US 3607276 A
Description (OCR text may contain errors)
United States Patent Shingo Ooue Saitama;
Hiroyuki Ueda, Saitama; Yoshihide Ilayakawa, Kanagawa, all of Japan Inventors Appl. No. 705,457 Filed Feb. 14, 1968 Patented Sept. 21, 1971 Assignee Fuji Photofllm Co., Ltd.
Kanagawa, Japan Priority Feb. 14, 1967 Japan 9420-67 PROCESS FOR MAKING METAL-GLOSSY IMAGES AND PROJECTION USING THE SAME 5 Claims, 1 Drawing Fig.
 References Cited UNITED STATES PATENTS 3,291,608 [2/ l 966 Elins 96/66 3,149,970 9/1964 Weyde 96/48 Primary Examiner-J. Travis Brown Assistant Examiner-Edward C. Kimlin Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT: A process for making a metal-glossy image which comprises treating a silver halide image with a solution containing physical developing nuclei and then treating the silver halide image thus treated with a solution containing a solvent for silver halide. A projection process which comprises treating a silver halide image 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.
PATENTEU SEP21 r971 INVENTORS' SHINGO OOUE HIROYUKI UEDA YOSHIHIDE HAYAKAWA BY fugumfotlwzw, H/MZM f/Vnrpeak ATTORNEYS PROCESS FOR MAKING METAL-GLOSSY IMAGES AND PROJECTION USING THE SAME 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 and an image projection process comprising applying an illuminating light for transmission and for reflection to said metalglossy image while varying the light intensity ratio, synthesizing the transmitted light and reflected light and projecting on a screen to thus obtain projected images varying in the contrast leading to a reversal 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 expression within a specified region of density. in a developing treatment, for example, an image having too high a contrast is obtained with a treatment which is too long, while an image having too low a contrast is obtained with a treatment which 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, the automatic printing of a printing paper, printing of a movie film, etc. are thereby much enhanced. The reason is that in an automatic printing machine using a paper roller, 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 can be freely varied by an optical system of the printing machine. The same is true of the 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 quenching phenomenon exhibited by fluorescent materials, etc., but these have disadvantages, such as complex structure, high production cost, a rather dark image for practical use as an enlarger, and lowered sharpness of the image.
It is an object of the invention to provide a process for making a metallic gloss image from a silver halide image wherein the reflection factor 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 the contrast leading to a reversal image by the use of such metalglossy image.
SUMMARY OF THE INVENTION More specifically, the former process consists in treating an image composed of silver halide with a solution containing physical developing nuclei and then treating with a developing solution containing a solvent for silver halide. The latter image projection process consists in applying an illuminating light for transmission and for reflection to the surface of the metal glossy image obtained by the former process while varying the light intensity ratio, synthesizing the transmitted light and reflected light and projecting on a screen to obtain projected images varying in the contrast leading to a reversal image.
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 the preparation thereof is easy.
Furthermore, it is possible to vary the contrast of an image or to reverse the same by giving simultaneously a transmission illumination and reflection illumination to the metal-glossy photographic image to cause image formation respectively and varying relatively the intensity of light of the transmission illumination and intensity of light of the reflection illumination, whereby a projected image having high brightness can be given on a screen.
In the metal-glossy image of the invention, not only the contrast of an image can be varied within a certain range by the foregoing optical system, but also, if a reflection illumination is applied to an image, such as by forming a negative image through a 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 light-sensitive 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 ofa slide or movie, etc.
DETAILED DESCRIPTION OF THE INVENTION The process for making a metal-glossy image according to the invention will now be illustrated in more detail.
The image having a metallic gloss according to the invention is obtained by treating an image composed of silver halide with a solution containing physical developing nuclei thereby to incorporate physical developing nuclei in a range of 0.001 to 0.2 micron in said silver halide image and then treating with a developing solution containing a solvent for silver halide.
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 process of the invention is projected on a screen while varying the contrast thereof. In optical system wherein image 1 is projected on light sensitive material for printing or screen 3 through projection lens 2, image I is subjected to transmission illumination by means of light source 4 for transmission illumination and condenser lens 5 for transmission illumination, while being subjected to reflection illumination by means of light source 6 for reflection illumination and halfsilvered mirror 8 (or partly reflecting and partly 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 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 transmission illumination and reflection illumination are different. If it is necessary to balance the color in such 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 on an image surface, E is the intensity of illumination of a reflection illumination light on the same, T is the transmittance of the image to an incident light beam and R is the reflectance, the brightness B of a projected image is given by the following relation:
where C is a constant determined by the F-number of a projected 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 [5 :0, that is utilizing only a reflecting light, B is proportional to R, for example, an ordinarily developed negative gives a reversed positive image. If selecting suitably the ratio of E and 13,, a desired contrast from negative to positive can 5 be obtained. If taking gamma as a value representative of the contrast, and K=ETIE +E as a value, representative of the ratio of E and E the change of gamma with K is shown in the following table, for example, with respect to the image obtained by the procedure of the example. ln table l, the gamma of negative character is plus and that of positive character is minus.
TABLE 1 Gamma Colloidal Silver Bath Silver s ma B th M h9. Method Advantages or effects of the photographic image having a metallic gloss according to the invention are summarized below.
l. 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.
2. 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 transmission illumination or reflection illumination is effected to a specified area of 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 in- 5 vention without limiting the same. The commonly used silver halide photographic sensitive material is also used therein. As the silver halide of the light-sensitive material, there are used one or more of silver bromide, silver chloride and silver iodide, above all, silver chloride being the most suitable to obtam a metallic gloss.
EXAMPLE The procedure for making the metal-glossy image of the invention are exemplified in the following. The steps from (1) to (7) are by the known process for making a photographic image composed of silver halide and those from (8) to (12) 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 5 minutes using a developing solution of the following composition:
\Vater'(50C.) 750 ml. Monomethyl-p-aminophenol l g. Anhydrous Sodium Sulfite 75 g. Hydroquinone 9 g. Sodium Carbonate Monohydrate 29 g. Potassium Bromide 6 g.
Water to L000 ml.
3. Water Washing 20 C., one minute (flowing) 4. Flxing is carried out at 20 C. for 3 minutes using a fixing solution of the following composition: 5
Solution l Water (50C.) 600 ml.
Sodium Thiosulfate 300 g. Solution ll Water (50C. 200 ml.
Anhydrous Sodium 'l'hiosull'atc l5 g. Glacial Acetic Acid l2 ml. Potassium Alum 20 g.
Solutions l and ll are prepared separately, cooled at room temperature. Solution II is added to Solution l little by little with stirring so that the total volume may be 1,000 ml. 5. Water Washing at 20 C. for 5 minutes (flowing) 6. Bleaching is carried out at 20 C. for 3 minutes using a bleaching solution of the following composition:
Water 600 ml. Potassium Bichromate 20 g. Hydrochloric acid (30%) 50 ml.
Water To L000 ml.
A bleaching solution is preferably used capable of forming silver chloride.
7. Cleaning Bath lmmersing in 5 percent NaCl solution at 20 C. for 2 minutes. This procedure may be omitted, but should be carried out if possible in order to obtain a good result.
The foregoing procedures are conducted to form an image of silver halide and the following procedures (8), (9), and l0) constitute a main part of the process of the invention.
8. Swelling lmmersing in water at 60 C. for 1 minute to swell the emulsion layer. This procedure may be omitted, but should be carried out if possible in order to obtain a good result.
9. Physical Developing Nucleus Bath This treatment consists in immersing a sample in a treating solution contain ing physical developing nuclei. As such physical developing nuclei may be used colloidal metal particles such as colloid silver and colloid gold, colloidal metal sulfide particles such as colloid silver sulfide, colloid zinc sulfide, colloid nickel sulfide and colloid gold sulfide and colloidal sulfur. The particles have preferably a size of 0.00l to 0.2 micron. Treatment using colloid silver (9) a and using colloid silver sulfide (9) b are given for example.
9a. Colloidal Silver Bath The sample is immersed in a solution containing, for instance, 0.3 g. of colloid silver per 1,000 ml. at 40 C. for 10 minutes. The colloid silver is prepared by the known process, for example, by reducing silver nitrate in a gelatin solution with amidol or by reducing a silver chloride emulsion with hydrazine. colloidal silver particles ranging in size from 0.01 to 0.08 micron give good results. The treating solution contains preferably 0. l0.6 g. of colloid silver per 1,000 ml.
9b. Colloidal Silver Sulfide Bath The sample is immersed in a treating solution containing, for instance, 0.05 g. of colloidal silver sulfide particles per l,000 ml. of water at 40 C. for 10 minutes. The colloidal silver sulfide particles are prepared by a known process comprising adding sodium sulfide to a thiosulfate complex of silver in gelatin. Col loidal silver sulfide particles ranging in size from 0.001 to 0.03 micron give good results. The amount of silver in the treating solution, used in the method using colloidal silver sulfide, is less than that in the method using colloidal silver. The treating solution contains preferably 0.0l0.5 g. of silver sulfide, in particular, 0.03-0.08 g. of silver sulfide per 1,000 ml.
l0. Metal-Glossy Development Development with the following composition at 30 C. for 4 minutes gives a metalglossy image:
Water 600 ml. l-Phenyl-B-pyrazolidone 1.7 g. Anhydrous Sodium Sulfite 60 g. Hydroquinone 20 g. Boric Acid 2.7 g. Sodium Carbonate (Monohydrate) 47.5 g. Potassium Bromide 105.7 g.
Water To L000 ml.
1 1. Water Washing 30 seconds, flowing water 12. Drying about minutes, hot air An image having a metallic gloss is obtained by the foregoing procedures. The metallic gloss of the image 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 ofincidence of 45 and the reflected light beam is measured in the normal direction of reflection having an angle of 45 in the plane ofincidence against a line vertical to the surface. A measured value of such specular reflectance is in this case, and is 100 in the case of a vacuum vapor deposition surface of aluminum. The larger this value, the more the metallic gloss. When a metal-glossy image has such degree of gloss, the contrast of the image can be sufficiently varied or a reversal image can be given by changing the ratio of intensities of the reflection, illumination and transmission illumination, as shown in table 1.
The solvent for 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 slats besides the well known solvents such as thiocyanate, ammonium salts, organic bases, etc.
Methods of making an image 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 sub jecting a silver image to bleaching, said silver image being obtained by developing and fixing a silver halide photographic light 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 which properties 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 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 ofsilvcr halide.
2. The second is an application of the printing method. That is a printing plate of 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 said 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 thus remove silver halide partly.
. 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 ofa solution containing silver halide. In some cases, a silver halide image may be obtained by writing an image directly on a lightsensitive material of silver halide in pen or brush by the use of a solvent for silver halide in place of an ink to thus remove silver halide partly.
The process of the invention is applicable to any of the images composed of silver halide made by the foregoing various 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 sup port and a 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 in a swellable silver halide emulsion comprising sequentially forming a silver halide image in said emulsion by imagewise exposing a light-sensitive silver halide emul sion, fixing said emulsion, and bleaching said emulsion,
2. subjecting said emulsion to a swelling treatment corresponding to immersing said emulsion in water at about 60 C. for about 1 minute,
3. treating said silver halide image with a solution containing physical developing nuclei and then 4. treating said silver halide image thusly treated with a solution containing a solvent for silver halide.
2. The process as claimed in claim 1 wherein said silver halide image is a silver chloride image.
3. The process as claimed in claim 1 wherein said physical developing nuclei are selected from colloidal silver, colloidal gold, colloidal silver sulfide, colloidal zinc sulfide, colloidal nickel sulfide, colloidal gold sulfide, and colloidal sulfur.
4. The process as claimed in claim 3 wherein the size of said colloidal particles is in the range of0.00l to 0.2 micron.
5. The process as claimed in claim 11 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.