EP0440367A1 - Photographisches lichtempfindliches Silberhalogenidmaterial von hoher Empfindlichkeit und hoher Schärfe - Google Patents

Photographisches lichtempfindliches Silberhalogenidmaterial von hoher Empfindlichkeit und hoher Schärfe Download PDF

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Publication number
EP0440367A1
EP0440367A1 EP91300522A EP91300522A EP0440367A1 EP 0440367 A1 EP0440367 A1 EP 0440367A1 EP 91300522 A EP91300522 A EP 91300522A EP 91300522 A EP91300522 A EP 91300522A EP 0440367 A1 EP0440367 A1 EP 0440367A1
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EP
European Patent Office
Prior art keywords
light
high sensitivity
silver halide
exposure
sensitivity surface
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Granted
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EP91300522A
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English (en)
French (fr)
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EP0440367B1 (de
Inventor
Yasunori Wada
Haruhiko Sakuma
Masaaki Taguchi
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Konica Minolta Inc
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Konica Minolta Inc
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    • 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
    • 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

Definitions

  • This invention relates to a light-sensitive silver halide photographic material having high sensitivity and also excellent in sharpness of images, and an image-forming method and a photographing method of the same.
  • films for X-ray photography utilized in medical diagnoses are employed in combination with X-ray fluorescent intensifying screens at the time of photographing. This is because in consideration of influence of X-rays to human bodies, X-rays which have been transmitted through a front X-ray fluorescent intensifying screen are to be further utilized in a rear X-ray fluorescent intensifying screen for the purpose of utilizing X-rays effectively.
  • a light irradiated from one X-ray fluorescent intensifying screen is transmitted through an adjacent silver halide emulsion layer, and the light is scattered by a support to cause from both surfaces a so-called crossover exposure phenomenon that a silver halide emulsion layer on the other side is subjected to imagewise exposure, which becomes a great factor to deteriorate sharpness of images.
  • Japanese Unexamined Patent Publication No. 110538/ 1990 discloses a technique in which silver halide emulsion layers having different color sensitivities are provided on an A surface and a B surface, and X-ray fluorescent intensifying screens having emission spectra corresponding to the respective color sensitivities are used.
  • the present inventors have investigated variously a method for improving sharpness of a light-sensitive silver halide photographic material having a silver halide emulsion layer on both surfaces by making sensitivities and amounts of silver coated different between an emulsion layer at one side (A surface) and an emulsion layer at the other side (B surface) and using a X-ray fluorescent intensifying screen only at one surface, and consequently found that since the (A) surface and the (B) surface are composed of different emulsions, amounts of silver and amounts of a binder, respectively, surface physical properties of the (A) and (B) surfaces of a film are not balanced.
  • a first object of the present invention is to provide a light-sensitive silver halide photographic material having high sensitivity and also excellent in sharpness.
  • a second object of the present invention is to provide a light-sensitive silver halide photographic material for X-rays by which images can be obtained without slippage of images even in oblique photographing, and an image-forming method of the same.
  • a third object of the present invention is to provide a light-sensitive silver halide photographic material for X-rays having good film conveying property.
  • a fourth object of the present invention is to provide an image-forming method of a light-sensitive silver halide photographic material, in which a X-ray fluorescent intensifying screen is used only on one surface and exposure is effected only from one surface to obtain images with high sharpness when the light-sensitive material according to the present invention is exposed.
  • a fifth object of the present invention is to provide a photographing method which can facilitate distinction between a front surface and a rear surface of a film and prevent erroneous loading when the film according to the present invention is inserted into a cassette.
  • a light-sensitive silver halide photographic material having been provided at least one silver halide emulsion layer on respective surfaces of a transparent support, characterized in that when an exposure dose at a position of one surface is an exposure dose giving a density of a fog density + 1.60 after exposing from a high sensitivity surface of said light-sensitive material and developing under the following development processing conditions, a density at a position of the other surface corresponding to said position is a fog density + 0.20 or less.
  • Processing is carried out by using SRX 501 (trade name, produced by KONICA CORPORATION) with 45 seconds processing mode.
  • a temperature of the developing processing solution is 35 °C and that of the fixing solution is 33 °C.
  • water for washing is supplied with 4 liters per minute and a water temperature of 18 °C.
  • a drying temperature is 45 °C.
  • Atmosphere in which the automatic processor is installed is 25 °C and 60 % relative humidity.
  • a replenishing solution stock tank is charged 20 liters of water with a water temperature of 18 °C and under stirring, the above Part - A, Part - B and Part - C are successively added thereinto to make 38 liters of a solution having a pH of 10.53 at 25 °C.
  • the above starter is added to the solution with an amount of 20 ml per liter and the mixture is filled in a developing tank of the automatic processor available from KONICA CORPORATION.
  • a pH of the developing solution at this time is 10.26 at 25 °C.
  • the developing replenishing solution was replenished with an amount of 365 ml per 1 m2 of a sample of the present invention.
  • a replenishing solution stock tank is charged 20 liters of water with a water temperature of 18 °C and under stirring, the above Part - A and Part - B are successively added thereinto. Finally, water and acetic acid are added to make 38 liters of a solution having a pH of 4.20 at 25 °C. After allowing this fixing replenishing solution to stand at 25 °C for 24 hours, it is filled in a fixing tank of the automatic processor available from KONICA CORPORATION. A replenishing amount of the fixing replenishing solution is 640 ml per 1 m2 of a sample of the present invention.
  • An image-forming method comprising using a light-sensitive silver halide photographic material having been provided a silver halide emulsion layer on respective surfaces of a transparent support and also having both surfaces with different sensitivities, and carrying out a development processing by exposure with a light having a wavelength of 300 nm or more and a latent image-forming property from a high sensitivity surface side of said light-sensitive material.
  • the light-sensitive material having been provided a silver halide emulsion layer on respective surfaces of a transparent support and also having both surfaces with different sensitivities of above (2) wherein by an image-forming method in which a development processing is carried out by exposure with a light having a wavelength of 300 nm or more and a latent image-forming property from a high sensitivity surface side of said light-sensitive material, an amount of a light transmitted through a support from the high sensitivity surface and reaching to the interface between the support and the low sensitivity emulsion layer is 12 % or more and 75 % or less of an exposure amount to the high sensitivity surface.
  • the light-sensitive material having been provided a silver halide emulsion layer on respective surfaces of a transparent support and also having both surfaces with different sensitivities of above (2) wherein when exposure is effected with a light having a wavelength of 300 nm or more and a latent image-forming property from a high sensitivity surface side of said light-sensitive material, an amount of a light transmitted through a support from the high sensitivity surface and reaching to the interface between the support and the low sensitivity emulsion layer is 12 % or more and 75 % or less of an exposure amount to the high sensitivity surface, and when an exposure dose giving a density of a fog density + 1.60 after a development processing is given to the high sensitivity surface, a density at a position of the other surface corresponding to receiving the same exposure dose as said position is a fog density + 0.20 or less.
  • An image-forming method of the light-sensitive material having been provided a silver halide emulsion layer on respective surfaces of a transparent support and also having both surfaces with different sensitivities of above (2) by carrying out a development processing by exposure with a light having a wavelength of 300 nm or more and a latent image-forming property from a high sensitivity surface side of said light-sensitive material, wherein an amount of a light transmitted through a support from the high sensitivity surface and reaching to the interface between the support and the low sensitivity emulsion layer is 12 % or more and 75 % or less of an exposure amount to the high sensitivity surface.
  • An image-forming method of the light-sensitive material of above (2) wherein when images are formed by an exposure method in which exposure is effected by fluorescence of a light having a wavelength of 300 nm or more and a latent image-forming property irradiated by absorption of X-rays from a high sensitivity surface side, an amount of a light transmitted through a support from the high sensitivity surface and reaching to the interface between the support and the low sensitivity emulsion layer is 12 % or more and 75 % or less of an exposure amount to the high sensitivity surface.
  • An image-forming method comprising using a light-sensitive silver halide photographic material having been provided a silver halide emulsion layer or respective surfaces of a transparent support and also having both surfaces with different sensitivities, and effecting exposure with a light having a wavelength of 300 nm or more and a latent image-forming property only from a high sensitivity surface side of said light-sensitive material.
  • a light-sensitive silver halide photographic material having been provided a silver halide emulsion layer on respective surfaces of a transparent support and also having both surfaces with different sensitivities, characterized in that a sensitivity of a high sensitivity surface is 1.5 to 10 times as high as a sensitivity of a low sensitivity surface, and a G H (Ag/gelatin) value which is a weight ratio of silver to gelatin of said high sensitivity surface is larger than a G L (Ag/gelatin) value which is a weight ratio of silver to gelatin of the low sensitivity surface, and further a polyvalent alcohol compound is contained in an amount of 5.0 x 10 ⁇ 5 to 5.0 x 10 ⁇ 3 mole per gram of gelatin.
  • Fig. 1 shows plane views of a conventional film (a) with 10 x 12 inch size and a conventional cassette (a′) for said film for comparison
  • Fig. 2 is a side view of the cassette (a′) for the film.
  • Fig. 3 shows plane views showing three examples of the film with 10 x 12 inch size and the cassette for the film according to the present invention, wherein I represents a notch of the film, and I′ represents a part of the cassette coincident with the film in shape, which has substantially the same uneven shape as I of the corresponding film and II represents a hinge of the cassette.
  • Fig. 4 to Fig. 11 are characteristic curves of the light-sensitive silver halide photographic material obtained in Example 3 of the present invention.
  • X-ray photography is generally so conducted that an incident angle of X-rays relative to a film surface is 90°. However, X-ray photography is sometimes conducted at an oblique incident angle. In this case, the "slippage" of the front and rear surface images will be further enlarged, and also influence by crossover lights from the both surfaces as described above is exerted, whereby significant lowering in sharpness is brought about.
  • an emulsion layer is coated on both surfaces of a support, but the characteristic feature of the present invention resides in that light-sensitive emulsions on both surfaces have different sensitivities such a feature of which is different from the prior art and yet that photography is conducted by exposing only from one surface.
  • the sensitivity of the emulsion layer at one side (A surface) of the light-sensitive silver halide photographic material according to the present invention is preferably 1.5 times or more, more preferably 2.0 times to 10 times as high as the sensitivity of the emulsion layer at the other side (B surface).
  • the weight ratio of silver to gelatin of the (A surface) is required to be larger, preferably by 1.2 times or more, than the weight ratio of silver to gelatin of the (B surface).
  • the difference in sensitivity mentioned in the present invention is determined with a light source by which the light-sensitive material used in the present invention is photographed.
  • the difference in sensitivity of regular X-ray films can be measured by using a X-ray fluorescent intensifying screen for photographing regular X-ray films, and that of ortho X-ray films can be measured by using a X-ray fluorescent intensifying screen for photographing ortho X-ray films. If a system utilizing another light source (such as panchromatic and infrared rays) appears in the future, the difference in sensitivity will be measured by using a light source used in combination with a light-sensitive material.
  • another light source such as panchromatic and infrared rays
  • the value of sensitivity can be given as a reciprocal of X-ray dosage necessary for obtaining an optical density of 40 % of a maximum optical density (not including a support density) obtained by development.
  • the light-sensitive silver halide photographic material according to the present invention can be exposed from a high sensitivity surface side by using a light having a wavelength of 300 nm or more and a latent-image forming performance, followed by development, to obtain images.
  • light sources of 300 nm or more in light-sensitive materials for laser imagers, for examples, light sources of 820 nm and 780 nm which are wavelengths of laser beams for semiconductors, and those of 633 nm for He-Ne can be employed. They can be also applied to indirect X-ray films.
  • Another object of the present invention is to make a sensitivity of films for one surface exposure system higher.
  • a large amount of silver halide with a large grain size should be coated.
  • processing characteristics such as development, fixing, washing and drying are deteriorated, which goes against the present situation that photographic constituent layers have become thinner for rapid processings.
  • an amount of silver halide attached is preferably made large at a high sensitivity layer side.
  • a total amount of silver halide at the side constituting a high sensitivity layer is 1.1 times or more, preferably 1.2 times or more, but preferably 5 times or less as large as a total amount of silver halide at a low sensitivity layer side. If the ratio exceeds the above range, an advantage obtained by providing silver halide on both surfaces of a light-sensitive material for the purpose of one surface exposure as in the present invention cannot be exhibited effectively.
  • an amount of a light transmitted through a support from a high sensitivity surface and reaching to a low sensitivity surface is preferably larger than that of a both surface type light-sensitive material for X-ray photography.
  • a transmitted light of a light source used is preferably in the range of 12 % to 75 %, more preferably 16 % to 65 %. If a transmitted light is increased exceeding the above range, deterioration of sharpness is brought about.
  • At least one polyvalent alcohol compound is preferably contained in an amount of 5.0 x 10 ⁇ 5 to 5.0 x 10 ⁇ 3 mole per gram of gelatin in constituent layers of said light-sensitive material.
  • the polyvalent alcohol to be used in the present invention preferred is an alcohol having 2 to 12 hydroxyl groups in a molecule and having 2 to 20 carbon atoms, in which hydroxyl groups are not conjugated to each other with a conjugating chain, namely an alcohol of which an oxidized type chemical formula cannot be written. Further, an alcohol having a melting point of 50 °C to 300 °C is preferred.
  • S B ′/S B of the present invention is preferably 0.12 to 0.75.
  • S B ′/S B is defined as follows.
  • S B is a sensitivity of only the B surface when exposure is carried out only from the B surface (the low-sensitivity layer).
  • S B ′ is a sensitivity of only the B surface when exposure is carried out only from the A surface (the high-sensitivity layer). If it is less than 0.12, an amount of a transmitted light from a high sensitivity surface to a low sensitivity surface is small, and image-forming efficiency of a low sensitivity surface is extremely lowered undesirably.
  • the above compounds according to the present invention are each easily available as a commercial product.
  • the light-sensitive silver halide photographic material of the present invention contains gelatin in an amount of 1.5 g/m2 to 6.5 g/m2, preferably 2.0 g/m2 to 4.5 g/m2 per one surface thereof.
  • the present invention can be applied to conventional light-sensitive materials having an emulsion on one surface for CRT photography, photography with a laser printer or a laser imager and photography of chest.
  • the present invention is further characterized in that the light-sensitive material according to the present invention is exposed only from one surface.
  • a front surface or a rear surface of a film may be positioned at an X-ray incidence side, but a surface of a high sensitivity layer is preferably positioned at an incidence side.
  • a X-ray fluorescent intensifying screen When a X-ray fluorescent intensifying screen is used, it may be set at either a front side or a back side of a film, but a X-ray fluorescent intensifying screen is preferably set at a high sensitivity emulsion layer side, whereby the effect of the present invention can be exhibited favorably.
  • Silver halide grains to be used in the high sensitivity emulsion surface of the present invention are preferably silver iodobromide or silver iodochlorobromide having a silver iodide content of 3 mole % or less, and more preferably a silver iodochlorobromide emulsion comprising 0.1 to 2.5 mole % of silver iodide, 97.5 mole % or more of silver bromide and 0 to 2.0 mole % of silver chloride.
  • the amount of silver halide to be coated on the high sensitivity surface is preferably 4.0 g/m2 or less, more preferably in the range of 1.0 to 3.5 g/m2 calculated on silver, and the amount on the low sensitivity surface is preferably 3.0 g/m2 or less, more preferably in the range of 0.1 to 2.5 g/m2.
  • the fog mentioned in the present invention refers to the sum of a support density and a density of developed silver at unexposed portions after development processing, namely the so-called gross fog.
  • the maximum density of the high sensitivity surface of the light-sensitive material according to the present invention is preferably 1.9 or more, more preferably 2.0 to 3.4, when exposed from the high sensitivity surface.
  • the maximum density of the low sensitivity surface is preferably 0.4 or more, more preferably 0.5 to 2.5, when exposed from the low sensitivity surface.
  • the light-sensitive material of the present invention is so designed that a low density portion and a medium density portion (about a density of 2.0) are formed substantially only on the high sensitivity surface by an exposure from a high sensitivity surface side, and the low sensitivity surface is sensitized by the light transmitted through the high sensitivity surface and a support to form a high density portion.
  • a density region particularly useful for diagnoses is in the range of from a fog density to a density of 1.6 to 2.3.
  • a high density region having a density of 1.6 to 2.3 or more is utilized effectively not only for diagnoses at that portion, but also for easy observation of a portion useful for diagnoses at a density of 1.6 to 2.3 or less.
  • the high density portion may be formed of images which are formed by a crossover light only from one surface and having low sharpness without practical problems. Rather, by forming images at a density in the range of from a fog density to a density of 1.6 to 2.3 only on the high sensitivity surface, images which are not influenced by a crossover light at all and not lowered in sharpness even in oblique photography can be formed.
  • the light-sensitive material of the present invention is a light-sensitive material having a high sensitivity surface and a low sensitivity surface with different sensitivities, preferably a light-sensitive material in which substantial images are not formed on a low sensitivity surface at a low exposure region until a density of 1.6 to 2.3 is formed on a high sensitivity surface, depending on uses of a light-sensitive material.
  • a density of a low sensitivity surface is a density of (fog + 0.20) or less, images useful as diagnostic images and having extremely high sharpness at a low density region to a medium density region can be obtained.
  • the light-sensitive material of the present invention is used for forming images on the low sensitivity surface by a light transmitted through the high sensitivity surface, and therefore an amount of a transmitted light of a light from the high sensitivity surface to the low sensitivity surface is preferably larger than that of a both surface type light-sensitive material for X-ray photography used in general, preferably in the range of 12 % to 75 %.
  • values of sensitivity, gamma, fog and maximum density mentioned in the present invention are values determined by using processing agents and processing conditions described in Examples of the present invention.
  • the light-sensitive silver halide photographic material according to the present invention is characterized in that a silver halide emulsion layer is coated on both surfaces of a support and the emulsions on the front surface and the rear surface have different sensitivities.
  • the point different from the conventional both surface film system is that it is necessary for users to easily distinguish between a sensitivity of the front surface and a sensitivity of the rear surface during handling of a film, when a film and a X-ray fluorescent intensifying screen are loaded at the time of photography, or during development.
  • a light-sensitive surface of the film and a surface of a X-ray fluorescent intensifying screen are required to be brought into close contact with each other appropriately.
  • film makers have developed a film having a notch provided at a specific part thereof.
  • the problem can be solved by a system for X-ray photography in which said light-sensitive material and said cassette have substantially the same uneven shape.
  • the above cassette refers to a cassette generally used for X-ray photography which is a film container made of aluminum, carbon or lead.
  • Substantially the same uneven shape possessed by the cassette and the light-sensitive material refers to a state that a certain position of the light-sensitive material is notched within the range which does not impair a photographed image, and the cassette has a shape which is coincident with the shape of the film notch.
  • the shape and the position of the uneven shape are not particularly limited, but the size may be as small as possible within the range that the effect of the present invention can be obtained, and the position may be upper, lower, left and right, and yet the shape and the position by which coincidence between the film notch and the cassette notch is easily given are employed.
  • a conventional cassette to which an uneven substance (its shape is selected as desired) having a shape which is coincident with a shape of a film notch is attached may be employed.
  • Fig. 1 shows one example of plane views of a film and a cassette used at present.
  • (a) is a film
  • (a′) is a cassette for the film.
  • Fig. 2 is a side view of the cassette for the film used at present.
  • Fig. 3 shows plane views (three examples) of films and cassettes for the films used in the system for X-ray photography according to the present invention.
  • (b) is a plane view of a film having an emulsion coated on its surface and having a -shaped notch provided in the left corner
  • (b′) is a plane view of a cassette for said film having substantially the same shape as the film.
  • (c) is a film having a -shaped notch provided in its left corner
  • (c′) is a cassette for said film
  • (d) is a film having a -shaped notch provided in its left corner
  • (d′) is a cassette for said film.
  • a mark which absorbs X-rays is attached to a cassette so that a left side and a right side of a film photographed can be recognized at the time of observation after development.
  • the photographing system of the present invention it is not necessary to attach such a mark, and there is an advantage that a photographed position is easily recognized by a film notch.
  • the point different from the prior art is that an uneven position of a film can be recognized by a cassette shape itself even when seen from outside. Accordingly, it has been found that the present invention is extremely useful not only for preventing erroneous loading, but also for preventing wrong diagnoses because of its advantage at the time of photography and observation.
  • the cassette for the film according to the present invention may be a cassette comprising the same material and the same constitution as those conventionally used, but preferably a cassette in which a film-receiving frame having a shape coincident with an uneven shape of the film is provided, more preferably a cassette also having an outer frame of which a shape is coincident with an uneven shape of the film, whereby the effect of the present invention can be exhibited more favorably.
  • a cassette in which a film-receiving frame having a shape coincident with an uneven shape of the film is provided, more preferably a cassette also having an outer frame of which a shape is coincident with an uneven shape of the film, whereby the effect of the present invention can be exhibited more favorably.
  • the cassettes shown in Fig. 3 not only the inner frames but also the outer frames have an uneven shape so that the inner uneven shape can be recognized from the outer uneven shape.
  • an outer frame may not have an uneven shape.
  • a seal may be attached to an outer surface of a cassette so that an uneven position within a cassette can be recognized.
  • the emulsion to be used in the light-sensitive silver halide photographic material of the present invention may be any silver halide such as silver iodobromide, silver iodochloride and silver iodochlorobromide, but particularly preferably silver iodobromide for obtaining high sensitivity.
  • the silver halide grains in the photographic emulsion may have any shape such as cubic, octahedron and tetradecahedron which grow in an isotropic manner, or a polyhedral crystal such as sphere and a twin having defects in phases or a mixture or complex thereof.
  • the silver halide grains may be fine grains having a grain size of 0.1 ⁇ m or less to greater grains having that of 20 ⁇ m or less.
  • the emulsion to be used in the light-sensitive silver halide photographic material of the present invention can be prepared according to a known method.
  • the emulsion can be prepared according to "1. Emulsion Preparation and types" disclosed on pp. 22 to 23 of Research Disclosure (RD) No. 17643 (December, 1978) and the method disclosed on p. 648 of RD No. 18716 (November, 1979).
  • the emulsion used in the light-sensitive silver halide photographic material according to the present invention can be prepared according to, for example, the methods disclosed on pp. 38 to 104 of "The theory of the photographic process", 4th edition, written by T.H. James, published by MacMillan Co. (1977), "Photographic Emulsion Chemistry” written by G.F. Dauffin, published by Focal Press Co. (1966), "Chimie et physique photographique” written by P. Glafkides, published by Paul Montel Co. (1967) and "Making and coating photographic emulsion” written by V.L. Zelikman et al, published by Focal Press Co. (1964).
  • the emulsion can be prepared under a solution condition such as a neutral method, an acidic method and an ammoniacal method, a mixing condition such as a normal precipitation, a reverse precipitation, a double jet method and a controlled double jet method and a grain preparation condition such as a conversion method, a core/shell method and a combination thereof.
  • a solution condition such as a neutral method, an acidic method and an ammoniacal method
  • a mixing condition such as a normal precipitation, a reverse precipitation, a double jet method and a controlled double jet method
  • a grain preparation condition such as a conversion method, a core/shell method and a combination thereof.
  • a monodispersed emulsion in which silver iodide is localized internally of grains can be mentioned.
  • the silver halide emulsion to be used preferably in the present invention there may be mentioned a monodispersed grain comprising an inner portion with a high iodine content as disclosed in, for example, Japanese Unexamined Patent Publications No. 177535/1984, No. 116347/1986, No. 132943/1986, No. 49751/1988 and No. 85846/1990.
  • a crystal habit of the crystal may be cubic, tetradecahedral or octahedral, and (1,1,1) face and (1,0,0) face which are intermediate therebetween may exist arbitrarily.
  • the monodispersed emulsion herein mentioned refers to a silver halide grain wherein when an average grain diameter is measured according to a conventional method, at least 95 % of grains in terms of grain number or weight have a grain diameter within ⁇ 40 %, preferably within ⁇ 30 % of the average grain size.
  • the grain size distribution of the silver halide may be either a narrow distribution as in a monodispersed emulsion or a wide distribution as in a polydispersed emulsion.
  • An inner portion and an outer portion of a crystalline structure of the silver halide may comprise different silver halide compositions.
  • the emulsion is a core/shell type monodispersed emulsion having a two-layered structure comprising a core portion with a high iodine content and a shell layer with a low iodine content.
  • the content of silver iodide in the portion with a high iodine content is preferably 20 to 40 mole %, particularly preferably 20 to 30 mole %.
  • a method for preparing such a monodispersed emulsion is known in the art, and disclosed in, for example, J. Phot. Sci. 12, pp. 242 to 251 (1963), Japanese Unexamined Patent Publications No. 36890/1973, No. 16364/1977, No. 142329/ 1980 and No. 49938/1983, U.K. Patent No. 1,413,748, U.S Patents No. 3,574,628 and No. 3,655,394.
  • a seed crystal is used as a growth nucleus and the seed crystals are grown by supplying silver ions and halide ions.
  • a method for obtaining a core/shell emulsion is disclosed in detail in, for example, U.K. Patent No. 1,027,146, U.S. Patents No. 3,505,068 and No. 4,444,877, and Japanese Unexamined Patent Publication No. 14331/1985.
  • Another grain form of the silver halide emulsion to be used in the present invention is preferably a tabular grain having an aspect ratio of 3 or more.
  • the above emulsion may be any type of emulsions such as a surface latent image type in which an latent image is formed on a grain surface, an internal latent image type in which a latent image is formed internally of a grain or a type in which a latent image is formed both on a grain surface and internally of a grain.
  • a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof and an iron salt or a complex salt thereof may be used.
  • the emulsion may be subjected to washing by a noodle washing method or a flocculation sedimentation method.
  • a noodle washing method for example, a method by using an aromatic hydrocarbon type aldehyde resin containing a sulfo group as disclosed in Japanese Patent Publication No. 16086/1960 and a method by using exemplary compounds G3 and G8 of a coagulating polymeric agent as disclosed in Japanese Unexamined Patent Publication No. 158644/1988, which are particularly preferred desalting methods.
  • the suitable support is a plastic film.
  • a prime-coating layer may be provided on a surface of the support or a surface of the support may be subjected to corona discharging or UV irradiation. On both surfaces of the support thus treated, the emulsion according to the present invention can be coated.
  • Monodispersed emulsion grains comprising silver iodobromide containing 2.0 mole % of silver iodide with an average grain size of 0.2 ⁇ m and having a shape of cubic and good variation coefficient which is a measure of mono-dispersibility of 0.15 were used as a nucleus, and silver iodobromide containing 30 mole % of silver iodide was grown at pH 9.8 and pAg 7.8.
  • emulsions comprising 4 kinds of tetradecahedral monodispersed emulsion grains comprising silver iodobromide with an average silver iodide content of 2.2 mole %, having average grain sizes of 0.375 ⁇ m, 0.64 ⁇ m, 1.22 ⁇ m and 1.88 ⁇ m, respectively, and having coefficients of variation of 0.17, 0.16, 0.16 and 0.17, respectively.
  • emulsions were called 1 -1, 1 -2, 1 -3 and 1 -4, respectively.
  • the emulsions were subjected to desalting to remove excessive salts according to a conventional coagulation method. Specifically, to the emulsions maintained at 40 °C, a formalin condensate of sodium naphthalenesulfonate and an aqueous solution of magnesium sulfate were added to effect coagulation, and a supernatant was removed.
  • a solution of 0.60 mole of potassium bromide and silver nitrate was added at a homogeneous flow for about 5 minutes until pBr reached to 3.0. (about 6.6 % of total silver nitrate used was consumed.) The total amount of silver nitrate consumed was about 11 mole.
  • an emulsion 2 containing tabular silver iodobromide grains with an average grain diameter of 1.80 ⁇ m and having an aspect ratio of about 9 : 1 was prepared. 80 % or more of total projected area of the silver iodobromide grains were tabular grains.
  • ammonium thiocyanate was added in amounts of 4 x 10 ⁇ 3 mole to 1 -1, 2 x 10 ⁇ 3 mole to 1 -2, 1 x 10 ⁇ 3 mole to 1 -3, 1.6 x 10 ⁇ 3 mole to 1 -4 and 3 x 10 ⁇ 3 mole to 2 per mole of silver, and further appropriate amounts of chloroauric acid and hypo were added to initiate chemical ripening.
  • the chemical ripening was effected under the conditions of a pH of 6.15 and a silver potential of 50 mV.
  • potassium iodide Fifteen minutes before completion of the chemical ripening (70 minutes after initiation of the chemical ripening), potassium iodide was added in an amount of 200 mg per mole of silver. After 5 minutes, 10 % (weight/volume) acetic acid was added to lower the pH to 5.6, and then the pH value was maintained for 5 minutes. Subsequently, a 0.5 % (weight/volume) solution of potassium hydroxide was added to return the pH to 6.15, and then 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to complete the chemical ripening.
  • Emulsions 1 -1, 1 -2, 1 -3, 1 -4 and 2 obtained were mixed as shown in Table 1, and to the mixtures, additives for emulsion described below were added to obtain preparation solutions.
  • a solution of sodium carbonate and potassium bromide was used for preparation so that photographic emulsion coating solutions had a pH of 6.40 and a silver potential of 74 mV (35 °C) after preparation.
  • samples were prepared in the following manner. Specifically, the photographic emulsion layer was prepared to contain gelatin in an amount of 2.0 g/m2 at both a high sensitivity emulsion layer side and a low sensitivity emulsion layer side, and silver halide in an amount calculated on silver as shown in Table 1.
  • a protective layer solution was prepared.
  • the protective layer was coated with the emulsion layer prepared as above by two slide hopper type coaters simultaneously on both surfaces of a support at a speed of 80 m/min so that an amount of gelatin attached became 1.15 g/m2, followed by drying for 2 minutes and 20 seconds, to obtain samples.
  • the spectral sensitizing dyes used for the preparation of the samples are shown below.
  • Spectral sensitizing dye B The additives used in the emulsions (light-sensitive silver halide coating solutions) are shown below. The amounts added are represented in an amount per mole of silver halide.
  • the additives used in the protective layer solution are shown below.
  • the amounts added are represented in an amount per liter of the coating solution.
  • Dye The above dye was weighed with a balance, and 10 kg of the dye was dissolved at 55 °C in a solvent comprising 28 l of tricresyl phosphate and 85 l of ethyl acetate. This solution was called an oily solution.
  • 270 ml of a 9.3 % aqueous gelatin solution in which 1.35 kg of an anionic surfactant (AS shown below) was dissolved at 45 °C was prepared. This solution was called an aqueous solution. (AS)
  • the oily solution and the aqueous solution described above were placed in a dispersing vessel, and dispersed while controlling a solution temperature to be maintained at 40 °C.
  • All of the average grain sizes per unit area of the dispersion obtained were within the range of 0.12 to 0.14 ⁇ m.
  • the photography was conducted by irradiating X-rays at a voltage in tube of 90 KVP and a current of 20 mA for 0.05 sec, and a sensitometry curve was prepared according to a distance method to determine a sensitivity, a maximum density and gamma.
  • the development was carried out by an automatic developing machine SRX-501 (trade name, manufactured by Konica Corporation) by using a developing solution and a fixing solution having the compositions described below at a developing temperature of 35 °C and a fixing temperature of 33 °C.
  • the washing water was supplied at a temperature of 18 °C in an amount of 1.5 l/min.
  • the whole processing steps were carried out in a 45 second mode.
  • the sensitivity of the A surface can be obtained by removing the light-sensitive layer at a B surface side from Sample (I) by proteinase, and similarly, the sensitivity of the B surface can be obtained by removing the light-sensitive layer at an A surface side from Sample (II). Further, the total sensitivity can be also obtained from Sample (I).
  • the sensitivity values were determined as a reciprocal of an X-ray dosage necessary for obtaining a density value which was calculated by multiplying the value obtained by subtracting a support density from a maximum density by 0.4 and adding a support density to the product.
  • sensitivities were measured in the same manner as above. The values are represented in a relative sensitivity when the sensitivity of Sample No. 1 was defined as 100. (the same may be said of Examples 2 to 5)
  • Sample No. 1 was subjected to a conventional exposure by using X-ray fluorescent intensifying screens on both surfaces since Sample No. 1 had the same emulsion constituent layer as a conventional X-ray film of both surface type.
  • the gamma values are represented in a reciprocal of a difference between reciprocals of logarithms of X-ray dosages giving densities of 1.0 and 2.0.
  • the photography was conducted at a voltage in tube of 90 KVP by using a X-ray fluorescent intensifying screen KO-250 only at a high sensitivity emulsion layer side according to the single back method.
  • the same procedures (the same procedures by using the same automatic developer, processing agent, processing temperature and processing time) were carried out as in the above sensitometry curve.
  • a sharp funk test chart SMS5853 (trade name, available from Konica Medical K.K.) was used for measuring sharpness. The procedures were carried out by using the same voltage in tube and X-ray fluorescent intensifying screen and under the same conditions as in the actual photography.
  • the developing solution and the fixing solution were used in an automatic developer 24 hours after each preparation.
  • S B in Table 1 is a sensistivity of the light-sensitive layer of the B surface.
  • S B′ is an apparent sensitivity obtained by the images at a B surface side obtained by removing the light-sensitive layer at an A surface side from Sample (I) described above.
  • S B′ /S B corresponds to a ratio of an amount of a light transmitted through the light-sensitive layer of the A surface and the support and reaching to the B surface to an amount of a light incident on the A surface when exposure is effected from an A surface side.
  • Table 2 in Samples No. 7, No. 8, No. 9 and No. 10 of the present invention, high sensitivity could be obtained even in one surface photography, and sharpness was excellent.
  • Sample No. 5 when the high sensitivity emulsion layer was fog density + 1.60, the low sensitivity emulsion layer took fog density + 0.20 or higher so that sharpness was not so good.
  • Example 2 By using the silver halide grains prepared in Example 1, a medical imaging film for CRT (cathode ray tube) photography was prepared.
  • the emulsion additive, the protective film recipe, the support to be used and the drying condition were the same as in Example 1. Further, the developing procedures were the same as in Example 1.
  • Backing dyes shown below were added to both layers of the emulsion layer and the protective layer at a low sensitivity emulsion layer side so as to be contained in amounts shown below.
  • a test of drying characteristics was conducted by processing the samples in a 45 second processing mode by using an automatic developer SRX-501 (trade name, manufactured by KONICA CORPORATION).
  • a temperature and a relative humidity at the place where the automatic developer was set were 25 °C and 62 %, respectively.
  • a temperature of a drying air of the automatic developer was set at 43 °C.
  • Example 2 By using the silver halide emulsions prepared in Example 1, the emulsions were prepared by mixing as shown in Table 5, and a coating solution was prepared accordint to entirely the same manner as in Example 1 to prepare film samples shown in Table 6.
  • Fig. 4 to Fig. 11 show characteristic curves of the samples of the present Example.
  • the characteristic curves of the high sensitivity emulsion layers in the Figures were obtained by measuring images only on the high sensitivity emulsion layers obtained by removing the rear surface (low sensitivity) emulsion layers by proteinase from the samples developed by exposing from a high sensitivity emulsion layer side.
  • the characteristic curves of the low sensitivity emulsion layers were obtained by measuring images only on the low sensitivity emulsion layers obtained by removing the rear surface (high sensitivity) emulsion layers by proteinase from the samples developed by exposing from a high sensitivity emulsion layer side.
  • the sensitivity values in Table 6 were determined as a reciprocal of an X-ray dosage necessary for obtaining a density of 1.0, and are represented in a relative sensitivity when the sensitivity of Sample No. 1 was defined as 100.
  • Sample No. 1 was subjected to a conventional exposure by using a X-ray fluorescent intensifying screen on both surfaces since Sample No. 1 had the same emulsion constituent layer as a conventional X-ray film of both surface type.
  • This emulsion was used as a seed grain, and grown in the following manner.
  • aqueous gelatin solution maintained at 40 °C, and to the mixture were added aqueous ammonia and acetic acid to adjust a pH to 9.5.
  • ammoniacal silver ions and a solution containing potassium iodide and potassium bromide were added according to a double jet method to give a silver iodobromide emulsion containing 30 mole % of silver iodide.
  • the above sensitizing dye (A) and sensitizing dye (B) were added in amounts of 300 mg and 15 mg, respectively, per mole of silver in the emulsion.
  • the emulsion obtained was maintained at 40 °C, and an appropriate amount of a formalin resin of sodium naphthalenesulfonate (average polymerization degree: 4 to 6) was added therein to sediment silver halide grains. After removal of a supernatant, pure water at a temperature of 40 °C was added, and then magnesium sulfate was added to sediment silver halide grains again, followed by removal of a supernatant.
  • a formalin resin of sodium naphthalenesulfonate average polymerization degree: 4 to 6
  • ammonium thiocyanate, chloroauric acid and hypo were added, and chemical ripening was effected under the conditions so as to obtain a maximum density.
  • the emulsion obtained in the above (B) was chemically sensitized. Specifically, ammonium thiocyanate, chloroauric acid and hypo were added to effect gold-sulfur sensitization.
  • Emulsion (B) After completion of this chemical sensitization, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added. Subsequently, by adding 150 mg/mole of AgX potassium iodide and the same amounts of the above sensitizing dyes (A) and (B) as in the case of Emulsion (A-1), spectral sensitization was effected. The emulsion obtained was called Emulsion (B).
  • Additives used in the respective emulsion solutions (light-sensitive silver halide coating solutions) of (A - 1), (A -2) and (B) are shown below. The amounts added are represented in an amount per mole of silver halide.
  • the additives used in the protective layer solution are shown below.
  • the amounts added are represented in an amount per gram of gelatin.
  • the above coating solutions were coated on both surface of a blue-colored polyethylene terephthalate film base with a thickness of 180 ⁇ m previously subjected to subbing treatment, followed by drying, to obtain Samples No. 1 to No. 11 shown in Table 9-1.
  • Emulsion (A-1) On the (A surfaces) of Samples No. 1 to No. 9 was used Emulsion (A-1), and on the (A surfaces) of Samples No. 10 and No. 11 was used Emulsion (B). On all the (B surfaces) was used Emulsion (A-2).
  • An MTF chart made of lead having 0.5 to 10 line/mm of square waves was brought in close contact with a rear surface at a front side of a X-ray fluorescent intensifying screen, and X-rays were irradiated so that a density of both surfaces of film portions which were not shielded by the chart made of lead became about 1.0.
  • the sharpness values in Table 8 were obtained by conducting photographing four extremital bone phantom obliquely at an X-ray incident angle of 30°, carrying out the same processings as described above, observing the images obtained with eyes and evaluating them by using the following 5 ranks.
  • a curling degree of the samples obtained was evaluated by using the following 5 ranks.
  • A indicates that a sample is the lowest in curling degree and the most excellent.
  • the images obtained were excellent in sharpness and had high sensitivity.
  • a light-sensitive silver halide photographic material having high sensitivity and high sharpness, and also improved in automatic conveying property could be obtained.
  • a light-sensitive silver halide photographic material and a method for photography of the same wherein images having high sharpness can be obtained by using a X-ray fluorescent intensifying screen only on one surface and effecting exposure only from one surface.
  • a method for X-ray photography which can facilitate distinction between a front surface and a rear surface of a film and prevent erroneous loading when a film is inserted into a cassette.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP91300522A 1990-01-23 1991-01-23 Photographisches lichtempfindliches Silberhalogenidmaterial von hoher Empfindlichkeit und hoher Schärfe Expired - Lifetime EP0440367B1 (de)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0501423A1 (de) * 1991-02-27 1992-09-02 Konica Corporation Röntgenmaterial
EP0520409A1 (de) * 1991-06-26 1992-12-30 Konica Corporation Photographisches, lichtempfindliches Silberhalogenidmaterial in Bezug auf Bildqualität und Gradation anpassbar photographischen Zwecken und Bilderzeugungsverfahren dafür
EP0524650A2 (de) * 1991-07-25 1993-01-27 Konica Corporation Röntgenmaterial mit variablem Kontrast
EP0530117A1 (de) * 1991-08-16 1993-03-03 Eastman Kodak Company Für die Abbildung von Fleisch und Knochen geeignete radiographische Elemente mit minimalem Cross-over Effekt
WO1998021625A3 (en) * 1996-11-10 1998-11-05 Smartlight Limited Wide latitude film
EP1246005A1 (de) * 2001-03-29 2002-10-02 Agfa-Gevaert Photographisches Silberhalogenid-Material für die Mammographie
US6573019B1 (en) 2001-03-29 2003-06-03 Agfa-Gevaert Photographic silver halide photographic material for mammography

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384633A2 (de) * 1989-02-23 1990-08-29 Eastman Kodak Company Radiographische Elemente mit ausgewählten Empfindlichkeitsverhältnissen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1226917B (it) * 1988-07-14 1991-02-22 Minnesota Mining & Mfg Combinazione di elementi fotosensibili da usare in radiografia.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384633A2 (de) * 1989-02-23 1990-08-29 Eastman Kodak Company Radiographische Elemente mit ausgewählten Empfindlichkeitsverhältnissen

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0501423A1 (de) * 1991-02-27 1992-09-02 Konica Corporation Röntgenmaterial
US5523198A (en) * 1991-02-27 1996-06-04 Konica Corporation Light-sensitive silver halide photographic material
EP0520409A1 (de) * 1991-06-26 1992-12-30 Konica Corporation Photographisches, lichtempfindliches Silberhalogenidmaterial in Bezug auf Bildqualität und Gradation anpassbar photographischen Zwecken und Bilderzeugungsverfahren dafür
US5268251A (en) * 1991-06-26 1993-12-07 Konica Corporation Light-sensitive silver halide photographic material image quality- and gradation-adaptable to photographing purposes and image forming method therefor
EP0524650A2 (de) * 1991-07-25 1993-01-27 Konica Corporation Röntgenmaterial mit variablem Kontrast
EP0524650A3 (en) * 1991-07-25 1993-06-30 Konica Corporation Variable contrast x-ray material
EP0530117A1 (de) * 1991-08-16 1993-03-03 Eastman Kodak Company Für die Abbildung von Fleisch und Knochen geeignete radiographische Elemente mit minimalem Cross-over Effekt
WO1998021625A3 (en) * 1996-11-10 1998-11-05 Smartlight Limited Wide latitude film
EP1246005A1 (de) * 2001-03-29 2002-10-02 Agfa-Gevaert Photographisches Silberhalogenid-Material für die Mammographie
US6573019B1 (en) 2001-03-29 2003-06-03 Agfa-Gevaert Photographic silver halide photographic material for mammography

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DE69117779T2 (de) 1996-11-14
DE69117779D1 (de) 1996-04-18
EP0440367B1 (de) 1996-03-13
JP2847574B2 (ja) 1999-01-20
JPH04181238A (ja) 1992-06-29

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