Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes
  • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C2200/00—Details
  • G03C2200/58—Sensitometric characteristics

Definitions

• the present invention relates to a silver halide light-sensitive material for X-ray photography which enables intended photographic properties to be obtained with one and the same light-sensitive material.
• X-ray films manufactured by Konica Corp. include SR-G for ordinary X-ray examination, high-speed SR-V for X-ray examination using a contrast medium, high-contrast SR-H or SR-HG, low-contrast SR-L for X-ray examination of a digestive organ, wide-latitude SR-C for X-ray examination of the chest, and highly sharp new-CM for X-ray examination of the breast.
• One object of the present invention is to provide a silver halide photographic light-sensitive material for X-ray photography, which enables intended photographic properties to be obtained, according to the purpose of photographing, with one and the same light-sensitive material.
• Another object of the present invention is to provide a highly-sensitive silver halide photographic light-sensitive material for X-ray photography, which enables an image with improved sharpness to be formed by simply changing the manner of combination of intensifying screen to be applied to the front and back of the light-sensitive material, as well as to provide a method of forming an image using said light-sensitive material.
• this amount should preferably be larger.
• the amount of light passing through the HS side exceeds 50%, the double-sided photographing will be accompanied by such problems as significant deterioration of image quality (in particular, sharpness) due to increased cross-over light, as well as insufficient manifestation of the effects of intensifying screen applied to each side of the film.
• the amount of light transmitted by the HS side should preferably be 12% to 50%, more preferably 14% to 35%.
• the amount of light passing through the LS sion side and arriving at the boundary between the support and the HS side should preferably be 0% to 35%, more preferably 12% to 30%.
• the amount of light transmitted by the LS side is required to be as small as possible in order to improve the sharpness of the HS side, where a middle- to high-density area is formed.
• the amount of light transmitted by the LS side can be decreased by the provision of a cross over light-preventing layer under the emulsion layer of the LS side or by the addition of a large amount of a dye to the emulsion layer of the LS side.
• this amount of light is extremely small, i.e., 10% or less, the image-forming efficiency will be lowered significantly when intensifying screen is applied only to the HS side.
• the S H '/S H ratio (the amount of light transmitted by the LS side) should preferably be 0.35 or less.
• the S H '/S H ratio can be minimized by providing a cross over light-preventing layer between the emulsion layer of the HS or the LS side and the support. The provision of such layer, however, may result in a lowering in sensitivity when intensifying screen is applied only to the HS side. Even when such layer is provided, the S H '/S H ratio should not be lower than 0.12. It is preferable to cut cross over light not by providing a cross over light-preventing layer but by increasing the light absorbing power of the emulsion layer itself.
• intensifying screen be applied to the HS side, or high-speed intensifying screen and low-speed intensifying screen be applied to the LS side and the HS side, respectively.
• the HS and LS sides have different photographic properties, and hence, discrimination between these sides is necessary.
• a notch may be provided.
• One emulsion side can be distinguished from the other more effectively by a difference in the amount of reflected safe light in the dark room.
• a fluorescent substance use is made of gadolinium sulfaoxide:terbium. To prevent sensitivity from lowering, therefore, a substance having a higher absorption to safe light, which normally consists of rays with wavelengths of 560 nm or more, should be added to one of the emulsion sides.
• Such substance examples include a coupler that has developed cyan (a color complementary to red) or a (bluish) green dye which exhibits a lower absorption to light of 545 nm in wavelength.
• This substance should preferably be added to an intended emulsion side in such an amount that the amount of safe light reflected by this emulsion side will be smaller than that reflected by the other emulsion side by 30% or more. Any substance will do, as long as it has no adverse effects on the photographic properties of a light-sensitive material, and as long as it absorbs light of 560 ⁇ m or more in wavelength.
• substances having high absorption for light with a wavelength ranging from 560 nm to 700 nm are used on one side of a support, they may also be used on both sides of the support.
• a solution obtained by dissolving a coupler that has developed a color or an anthraquinone-based dye in a high-boiling point organic solvent, or an aqueous solution of an oxanol-based dye (which is soluble in water, and is hardly adsorbed by a silver halide) can be added to an emulsion layer, a protective layer, an intermediate layer or a subbing layer of an intended emulsion side.
• a hydrophilic polymer which can be removed therefrom during the steps of development, fixing and rinsing e.g. polyvinyl alcohol, polyacrylic acid, polyacrylamide, dextran
• a hydrophilic polymer which can be removed therefrom during the steps of development, fixing and rinsing should preferably be added to the HS side in an amount of 0.1 to 2.5 g per square meter.
• the amount of a silver halide should preferably be 4.0 g per square meter of a light-sensitive material.
• each emulsion side is defined as the reciprocal of the amount of X-ray which is needed to obtain a density value which is expressed by: (Max. density - fogging density) ⁇ 0.4 + fogging density
• the maximum density of the HS side be 1.80 or more.
• the amount of cross over light passing through the HS side and arriving at the boundary between the LS side and the support should preferably be 35% or less.
• silver halide use can be made of any of conventional photographic silver halides, such as silver iodobromide, silver iodochloride and silver iodochlorobromide. Of them, silver iodobromide is especially preferable in respect of sensitivity.
• the shape of a silver halide grain is not limitative; isotrophic crystals such as cubic, octahedral and tetradecahedral crystals; polyhedral crystals such as spherical crystals; and crystals with defective sides such as twin crystals. A mixture or composite form of these crystals is also usable.
• the size of silver halide grains may be 0.1 ⁇ m to 20 ⁇ m.
• An emulsion to be used in the light-sensitive material of the invention can be prepared by known methods; for examples, by a method described in "Emulsion Preparation and Type", Research Disclosure No. 17643, December, 1978, pages 22 to 23; a method described in Research Disclosure No. 18716, November, 1979, page 648; a method described in T.H. James, "The Theory of the Photographic Process", Macmillan, 4th ed., 1977, pages 38 to 104; a method described in G.F. Dauffin, "Photographic Emulsion Chemistry", Focal Press, 1966; a method described in P.Glafkides, “Chimie et Physique Photographique", Paul Montel, 1967; and a method described in V.L. Zelikan et al., “Making and Coating Photographic Emulsion", Focal Press, 1964.
• a silver halide emulsion can be prepared while keeping the mixture of ingredients neutral (the neutral method), acidic (the acid method) or ammoniac (the ammonia method).
• the mixing of the ingredients may be performed by the single-jet method, the reverse-jet method, the double-jet method or the controlled double-jet method.
• Growing grains may be performed by the conversion method, the core/shell method, or the like.
• a silver halide emulsion is one that consists of monodispersed silver iodobromide grains in each of which silver iodide is localized in the interior portion.
• An emulsion disclosed in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 177535/1984, 802237/1986, 132943/1986 and 49751/1988, i.e., an emulsion consisting of monodispersed grains in each of which silver iodide is localized in the interior portion, can be employed preferably in the invention.
• the shape of a silver halide crystal may be cubic, tetradecahedral or octahedral.
• a crystal having the ⁇ 1,1,1 ⁇ face and the ⁇ 1,0,0 ⁇ face in combination may also be used.
• Monodispersed silver halide grains are defined as grains, at least 95% (by weight cut) of which having sizes falling within the range of 60 to 140% (preferably 70 to 130%) of the average grain size (see Japanese Patent O.P.I. Publication No. 162244/1985).
• the variation coefficient of such grains is 0.20 or less.
• polydispersed silver halide grains are also usable.
• silver halide grains with a silver iodide content of 2.5 mol% or less, a silver bromide content of 95.5 mol% or less and a variation coefficient of 0.30 or less.
• silver iodides in quantity of 60% or more of the total silver iodides contained in a total grain are contained in the inside portion of the grain corresponding to 30% of the grain volume.
• the preferable grain of the mono-dispersed emulsion of a core/shell type includes a normal crystal cube, a tetradecahedron, an octahedron, a sphere-shaped grain having both a ⁇ 1,1,1 ⁇ plane and a ⁇ 1,0,0 ⁇ plane together, or a tabular twin crystal wherein 50% or more of the projected area is of an aspect ratio ranging from 3 to 15.
• the aspect ratio in the invention means one obtained through a method described in Japanese Patent Application No. 99345/1989.
• the interior portion and exterior portion of a grain may differ in halide composition.
• a core/shell silver halide grain having a high-chloride interior portion (core) and a low-chloride exterior portion (shell) is preferable.
• the silver iodide content of the core should preferably be 10-40 mol%, more preferably 20-30 mol%.
• An emulsion comprising such core/shell type grains can be prepared by a known method (see J. Phot. Sci., Vol.12, 1963, pages 242 to 251, Japanese Patent O.P.I. Publication Nos. 36890/1973, 16364/1977, 142329/1980, 49938/1983, British Patent No. 1,413,748, U.S. Patent Nos. 3,574,628 and 3,655,394).
• a monodispersed emulsion obtained by using seed grains as growth nuclei is preferable. Formation of core/shell grains is described in detail in British Patent No. 1,027,146, U.S. Patent Nos. 3,505,068, 4,444,877 and Japanese Patent O.P.I. Publication No. 14331/1985.
• the project area of tabular silver halide grains with an average aspect ratio of 3 to 15 account for 50% or more of the total project area of silver halide grains.
• Tabular grains have such a merit that the amount of cross over light can be adjusted only by controlling the amount of a spectral sensitizing dye.
• tabular silver halide grains can be prepared by methods described in British Patent No. 2,112,157, U.S. Patent Nos. 4,439,520, 4,433,048, 4,414,310, 4,434,226, Japanese Patent O.P.I. Publication Nos. 113927/1983, 127921/1983, 138342/1988, 284272/1988 and 305343/1988.
• Silver halide grains may be such that a latent image is formed mainly in the inside or on the surface.
• Silver halide grains may be doped with a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a metal complex of iridium, a rhodium salt or a metal complex of rhodium, and an iron salt or a metal complex of iron, during physical ripening or grain growth.
• Silver halide grains may be rinsed to remove unnecessary soluble salts by the conventional noodle washing method or by the flocculation method.
• a sulfo group-containing aromatic hydrocarbon-based aldehyde resin disclosed in Japanese Patent Examined Publication No. 16086/1960 or high molecular flocculating agents (example compound Nos. G3 and G8) disclosed in Japanese Patent O.P.I. Publication No. 158644/1988.
• various additives may be added to a silver halide emulsion. Examples of usable additives include compounds described in Research Disclosure No. 17643 (December 1978), No. 18716 (November 1979) and No. 308119 (December 1989). See below.
• Suitable supports are plastic films.
• the surface of the support may be subbed to improve adhesion between the support and other layers, or may be subjected to a corona discharge treatment or a UV ray irradiation treatment.
• a light-sensitive material of the invention can also be applied to a light-sensitive material for photographing with a imaging camera used in photographing a hard copy of a medical diagnostic equipment, a light-sensitive material for photographing laser images, and to a light-sensitive material for photofluorography, and it can be provided with an aptitude for high sensitivity and rapid processing, maintaining its image quality which is as good as that of a single-sided emulsion-coated light-sensitive material.
• the variation coefficient was measured by the method described in Japanese Patent O.P.I. Publication No. 162244/1985.
• Pure water was added to each of emulsions (A) and (B) in an amount of 500 ml per mol silver, and heated to 50°C. Then, the following sensitizing dyes A and B were added in amounts of 300 mg and 450 mg, respectively, per mol silver halide. The weight ratio of A and B was 150:1.
• the chemical ripening was performed at a pH of 6.15 and a silver potential of 80 mV.
• each coating liquid was adjusted to 6.20 and 80 mV (35°C), respectively, by the addition of sodium carbonate and potassium bromide.
• a light-sensitive material sample was formed by the method described below.
• the amount of gelatin was adjusted to 2.1 g/m2 on each of the HS and LS sides.
• the amount of a silver halide was translated into the amount of silver (see Table 1).
• a coating liquid for a protective layer was prepared by using the following additives.
• the gelatin content of a protective layer was adjusted to 1.20 g/m2.
• the HS side, the LS side and the protective layer were formed by applying the coating liquids to a support by means of two slide hopper coaters. The coating liquids were applied to the both sides of the support simultaneously. The coating speed was 85 m/min.
• the coated support was dried for 2 minutes and 20 seconds, whereby a light-sensitive sample was obtained.
• the support was made of a 175 ⁇ m-thick polyethylene terephthalate film for X-ray photography that had been colored with blue (density: 0.15).
• the support had been subbed with an aqueous dispersion obtained by diluting a copolymer of glycidyl methacrylate (50 wt%), methyl methacrylate (10 wt%) and butyl methacrylate (40 wt%) with water such that the concentration of the copolymer would be 10 wt%.
• the following dye was used in the form of an aqueous solution of bluish green, which is the color complementary to red.
• a sheet of fluorescent sensitizing paper to be applied to the back of a light-sensitive material for X-ray photography (SRO-250, manufactured by Konica Corp.) was brought into contact with the high-speed emulsion side (side A) of sample No.1. The sample was then exposed to X-ray, and processed according to the method described below. The processed sample was designated as 1-I.
• Another sheet of the same sensitizing paper was applied to the low-speed emulsion side (side B) of sample No. 1, and the resultant was exposed to X-ray, and processed according to the method described below.
• the processed sample was designated as 1-II.
• X-ray exposure was performed for 0.08 second at 20 mA and 80 KVP (tube voltage).
• a sensitometry curve was formed by the distance method, and from this curve, sensitivity, maximum density and gamma value were obtained.
• processing was performed by means of an automatic developing machine (SRX-502, manufactured by Konica Corp.), and a developer and a fixer of the following compositions.
• the developing temperature and the fixing temperature were 35°C and 33°C, respectively.
• Rinsing was conducted by supplying 5 l per minute of 18°C water. The entire course of the processing was completed within 45 seconds.
• the sensitivity of the A side was obtained by removing the emulsion layer from the B side of sample 1-I with a protein decomposing enzyme. Similarly, the sensitivity of the B side was obtained by removing the emulsion layer from the A side of sample 1-II.
• Sensitivity was defined as the reciprocal of the amount of X-ray necessary to obtain a density which is represented by: (Max. density - fogging density ⁇ 0.4) + fogging density
• Sample No. 1 had the same emulsion layer structure as that of ordinary double-sided X-ray films, and hence, fluorescent sensitizing paper was applied to the both side thereof.
• the gradient was calculated from the reciprocal of numerical value obtained by multiplying the difference of cologarithms of X-ray dosages causing respectively (fog + 0.25 density) and (fog + 2.0 density) by 1/(2.00 - 0.25).
• Each of sample Nos. 1 to 20 was evaluated for sharpness by the following method.
• Sample Nos. 2 to 20 were prepared in substantially the same manner as in the preparation of sample No. 1, except that the type of film was varied to those shown in Table 2. Each sample was brought into contact with sensitizing paper. The type of sensitizing paper and the manner of combination of two sheets of sensitizing paper are as shown in Table 2. Using each sample, a Funk test chart (SMS5853, sold by Konica Medical Corp.) was photographed. The tube voltage was 80KVP. After exposure, each sample was processed in the same way as mentioned above.
• SMS5853 sold by Konica Medical Corp.
• the amount of X-ray was adjusted such that the average density of light and shade formed in the photograph would be 0.8 ⁇ 0.02.
• the developer and fixer were put in the automatic developing machine 24 hours after the preparation.
• Acrylic beads (diameter: 3 mm) and aluminum balls (diameter: 3 mm) were brought into close contact with each stage of a 20-stage aluminum penetrometer, and photographing was performed using each sample at a tube voltage of 90KVP. Then, the samples were processed in the same way as mentioned above. The graininess of an image in the density area of 0.5 to 1.2 (a density range where graininess can be observed most readily) was examined visually.
• the coating films had the following photographic properties.
• the HS and LS sides did not differ in emulsion layer properties and each had a relative sensitivity of 88.
• G H (the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3): 1.29
• G L (the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6): 1.21
• the HS and LS sides did not differ in emulsion layer properties and each had a relative sensitivity of 85.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 95 and 68, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 97 and 103, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 68 and 104, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 99 and 104, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 99 and 66, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 68 and 105, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 88 and 105, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 87 and 103, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 87 and 103, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• the HS and LS sides differed in emulsion layer properties and had relative sensitivities of 66 and 105, respectively.
• G H the gradient of a straight line connecting a fogging density + 0.5 and a fogging density + 1.3
• G L the gradient of a straight line connecting a fogging density + 0.3 and a fogging density + 0.6
• SRO-125, SRO-250 and SRO-500 fluorescent intensifying screen sold by Konica Corp.
• SRO-125, SRO-250 and SRO-500 fluorescent intensifying screen sold by Konica Corp.
• film Nos. I and II shown in Table 1 both sides of the support have the same properties
• the front side of the film was brought into contact with intensifying screen for the front
• the back side of the film was brought into contact with intensifying screen for the back.
• film Nos. III to XII the two sides of the support differed in properties
• each side of the film was brought into contact with intensifying screen for the back.
• Sensitivity was defined as the reciprocal of the amount of X-ray necessary for obtaining a fogging density + 1.0, and expressed as a value relative to that of sample 1 in Table 2, which was set as 80.
• the gradient was calculated from the reciprocal of numerical value obtained by multiplying the difference of cologarithms of X-ray dosages causing respectively (fog + 0.25 density) and (fog + 2.0 density) by 1/(2.00 - 0.25).
• the sensitivity of the LS side obtained when exposure is conducted from the HS side through fluorescent intensifying screen (S B ') and the sensitivity of the LS side obtained when exposure is conducted from the LS side through fluorescent intensifying screen (S B ) were each obtained by removing the sensitive layer from the HS side with a protein decomposing enzyme.
• the sensitivity of the HS side obtained when exposure is conducted from the LS side through fluorescent intensifying screen (S H ) and the sensitivity of the LS side obtained when exposure is conducted from the HS side through intensifying screen (S H ) were each obtained by removing the sensitive layer from the LS side with a protein decomposing enzyme.
• S L ', S L and S H were each defined as the reciprocal of the amount of X-ray needed to obtain a density which is defined as: (Max. density - fogging density) ⁇ 0.4 + fogging density.
• the system gamma was defined as the doubled difference between the logarithm of the reciprocal of the amount of X-ray that gave a fogging density + 0.8 and the logarithm of the reciprocal of the amount of X-ray that gave a fogging density + 1.3.
• sample No. 14 which was obtained by using film No. V (the maximum density of the HS side was below 1.80)
• the sharpness of an image in a density area of 1.6 or higher was poor when intensifying screen was applied only to the HS side.
• sample No. 18 which was obtained by using film No. VIII (the maximum density of the HS side was 1.80 or more)
• sample No. 18 had poor sharpness in a density area of 1.7 or more.
• Sample No. 19 though being a sample of the invention, had such a disadvantage that the contrast of the HS side was low. Therefore, when high-speed sensitizing paper and low-speed intensifying screen were applied to the LS side and the HS side, respectively, this sample produced an image which lacked sharpness due to poor contrast in a density area of 1.2 or less.
• X-ray photographs differing in contrast can be obtained with one and the same light-sensitive material only by changing the type of intensifying screen or the manner of combination of two sheets of sensitizing paper differing in luminescence. Therefore, the use of the light-sensitive material of the present invention eliminates the necessity of keeping various kinds of light-sensitive material to meet various needs, thus enabling investment control to be performed more readily and minimizing the possibility of misapplication of a film.

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• 1992
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