EP0437117A1 - Light sensitive silver halide photographic material improved in diagnosic properties - Google Patents
Light sensitive silver halide photographic material improved in diagnosic properties Download PDFInfo
- Publication number
- EP0437117A1 EP0437117A1 EP90314462A EP90314462A EP0437117A1 EP 0437117 A1 EP0437117 A1 EP 0437117A1 EP 90314462 A EP90314462 A EP 90314462A EP 90314462 A EP90314462 A EP 90314462A EP 0437117 A1 EP0437117 A1 EP 0437117A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- light
- sensitive
- silver halide
- layer
- sensitivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 52
- 239000004332 silver Substances 0.000 title claims abstract description 52
- -1 silver halide Chemical class 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 42
- 230000035945 sensitivity Effects 0.000 claims abstract description 38
- 239000000839 emulsion Substances 0.000 claims description 57
- 239000010946 fine silver Substances 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 48
- 239000000975 dye Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 238000011161 development Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 5
- 229910021612 Silver iodide Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 5
- 229940045105 silver iodide Drugs 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 150000004646 arylidenes Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910004829 CaWO4 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002969 morbid Effects 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000002601 radiography Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
-
- 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
Definitions
- This invention relates to a light-sensitive silver halide photographic material for medical use excellent in sensitivity and sharpness, and also improved in diagnostic properties.
- an object of the present invention is to provide a light-sensitive silver halide photographic material for medical use improved in sharpness without impairing sensitivity and also improved in diagnostic properties.
- Other objects of the present invention will be apparent from the following description.
- the present inventors have studied intensively to improve sharpness, and consequently found that the above object can be accomplished by the method described below, to accomplish the present invention.
- the object of the present invention can be accomplished by:
- a sensitivity of a light-sensitive silver halide photographic material refers to a value determined according to the following method.
- a sample exposed only from an A surface side is divided into two pieces. From one piece, a B surface is removed for measuring sA, and from the other piece, an A surface is removed for measuring sB'. Next, also from a sample exposed only from a B surface side, an A surface and a B surface are removed in the same manner for measuring sB and sA', respectively.
- characteristic curves are measured, and from the characteristic curves obtained, reciprocals of exposure dosages required for obtaining a density of base density + fog density + 1.0 are determined to obtain sA, sB, sA' and sB'.
- an exposure method varies depending on each light-sensitive material.
- the A surface and the B surface of the light-sensitive silver halide photographic material according to the present invention have a sensitivity of sA/sA' > 4.0, preferably 4.5 or more, more preferably 5.0 to 15.0.
- the sensitivity of the material is preferably sA/sB of 1.5 to 20, more preferably 2.5 to 10.
- At least one of the light-sensitive silver halide photographic emulsion layer and the hydrophilic colloidal layer at the B surface side contains at least one water-soluble dye.
- a silver halide grain at the B surface side As another method, as a silver halide grain at the B surface side, one kind of grains with a small grain size is used, or when a plural kinds of grains are mixedly used, these grains are combinedly used so as to become an average grain size of the mixture small.
- small means that the grain size of the B surface side is 70 to 80 % or less of that of the A surface side.
- water-soluble dye those generally known in the art can be employed.
- silver halide grains with a small grain size is used at the B surface side, and at least one of the above silver halide emulsion layer and the hydrophilic colloidal layer contains the dye as described above.
- a covering power mentioned in the present invention is a photographic density obtained by a predetermined amount of silver, and defined as described below.
- a covering power (C.P) is represented by the following formula:
- a ratio of the covering power of the A surface to that of the B surface of the light-sensitive silver halide photographic material according to the present invention is 1 : 1.5 or more (the covering power of the B surface is larger than that of the A surface), preferably 1 : 1.5 to 5.0, more preferably 1 : 1.5 to 2.0, the effect of the present invention can be exhibited favorably.
- the dye which can be used in the present invention include, for example, arylidene dyes disclosed in U.K. Patents No. 584,609 and No. 1,210,252, U.S. Patents No. 2,538,008, No. 2,538,009, No. 2,688,541 and No. 4,420,555, styryl dyes disclosed in Japanese Patent Publications No. 3082/1953, No. 16594/1969 and No. 28898/1984, merocyanine dyes disclosed in U.S. Patents No. 3,486,897, No. 2,706,193, No. 3,260,601 and No. 4,035,190, cyanine dyes disclosed in U.S. Patents No. 2,843,486, No. 3,294,539 and No.
- any layer may be selected, but the dye may be contained in at least one layer of a light-sensitive emulsion layer and other hydrophilic colloidal layers at the side where said emulsion layer is coated (e.g. non-light-sensitive layers such as an intermediate layer, a protective layer, a subbing layer and a mordant layer) or may be contained by dispersing therein.
- the dye may be contained in a silver halide emulsion layer or a layer nearer to a support than the silver halide emulsion layer or in both of these layers.
- the amount of the above dye to be added is preferably 0.2 mg/m2 to 150 mg/m2, more preferably 0.8 mg/m2 to 50 mg/m2.
- the dye can be introduced into a hydrophilic colloidal layer according to a conventional method.
- the dye is prepared to be an aqueous solution having an appropriate concentration, and when an emulsion layer is colored, the aqueous solution of the dye may be added in a silver halide emulsion or an aqueous hydrophilic colloidal solution before coating, and then coated.
- the dye according to the present invention may be carried within a layer by using a mordant.
- mordant which can make a dye nondiffusible by bonding at least one dye as described above to a mordant
- compounds disclosed in, for example, U.S. Patents No. 2,548,564, No. 2,675,316, No. 2,795,519, No. 2,839,401, No. 2,882,156, No. 3,048,487, No. 3,184,309, No. 3,444,138, No. 3,445,231, No. 3,706,563, No. 3,709,690 and No. 3,788,855 can be preferably used.
- nonionic surfactants known in the art may be used.
- the hydrophilic colloidal layer mentioned in the present invention refers to a hydrophilic layer provided in layers of a light-sensitive silver halide photographic material, and refers to various layers which contain a binder component such as gelatin and are necessary for a light-sensitive material for photography such as a silver halide emulsion layer, a protective layer, an intermediate layer, an antihalation layer, a filter layer, a development controlling layer, an UV absorbing layer and a prime-coating layer.
- a high sensitivity silver halide emulsion layer is coated as an A surface, and a protective layer containing gelatin as a binder component is provided thereon.
- a low sensitivity silver halide emulsion layer having a sensitivity different from that of the A surface is coated as a B surface.
- the water-soluble dye according to the present invention may be added and contained, and further, a hydrophilic colloidal layer (e.g. a gelatin layer containing a dye or a mordant layer on which a dye is carried) may be provided above or under said emulsion layer.
- 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 silver iodobromide is preferred since a light-sensitive material having a particularly high sensitivity can be obtained.
- the silver halide grains in the photographic emulsion may have any shape such as cube, octahedron and tetradecahedron which grow in an isotropic manner, or polyhedral crystal such as sphere and twin having defects in phases or a mixture or complex thereof.
- the silver halide grains may have a grain size of from 0.1 ⁇ m (fine particles) or less to 20 ⁇ m (big particles).
- the emulsion to be used in the light-sensitive silver halide photographic material of the present invention can be prepared according to the known method.
- the emulsion can be prepared according to "1. Emulsion Preparing Method (Emulsion Preparation and types)" disclosed at pp. 22 to 23 of Research Disclosure (RD) No. 17643 (December, 1978) and the method disclosed at p. 648 of RD No. 18716 (November, 1979).
- a monodispersed emulsion in which silver iodide exists locally internally of its grain can be mentioned.
- the monodispersed emulsion herein mentioned refers to silver halide grains wherein, for example, when an average grain diameter is measured according to the conventional method, at least 95 % of the grains in terms of the grain number or weight have a grain diameter preferably within ⁇ 40 %, more preferably within ⁇ 30 % of the average grain size.
- a grain size distribution of the silver halide may be a narrow distribution as in the case of a monodispersed emulsion or a wide distribution as in the case of a polydispersed emulsion.
- Crystalline structure of the silver halide may comprise different silver halide compositions at an inner portion and an outer portion.
- the emulsion is a core/shell type monodispersed emulsion having a clearly two-layered structure comprising a core portion with a high iodine content and a shell layer with a low iodine content.
- An amount of silver iodide in the portion with a high iodine content of the present invention is 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, Journal of Photographic Science, vol. 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, and U.S. Patents No. 3,574,628 and No. 3,655,394.
- the monodispersed emulsion as described above particularly preferred is an emulsion in which a seed crystal is used as a growth nucleus and grains are grown by supplying a silver ion and a halide ion.
- 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.
- the silver halide emulsion to be used in the present invention may be a tabular grain having an aspect ratio of 5 or more.
- Such a tabular grain have advantages that improvement in spectral sensitizing efficiency and improvement in graininess and sharpness of images can be accomplished, and it can be prepared according to the methods disclosed in, for example, U.K. Patent No. 2,112,157, and U.S. Patents No. 4,439,520, No. 4,433,048, No. 4,414,310 and No. 4,434,226.
- the above emulsion may be any emulsion of 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.
- cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof and iron salt or complex salt thereof may be used.
- the emulsion may be subjected to a noodle washing method, a flocculation sedimentation method or an ultra-filtration method.
- washing method there may be included, as particularly preferred desalting methods, a method of using an aromatic hydrocarbon type aldehyde resin containing sulfo group as disclosed in Japanese Patent Publication No. 16086/1960 and a method of using exemplary compounds G3 and G8 of a coagulating polymeric agent as disclosed in Japanese Unexamined Patent Publication No. 158644/1988.
- a 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 ray irradiation. On one surface or both surfaces of the support thus treated, the emulsion according to the present invention can be coated.
- the present invention can be applied to all light-sensitive silver halide photographic materials, but it is particularly suitable for high sensitivity black and white light-sensitive materials.
- a fluorescent screen composed mainly of a fluorescent substance which emits near ultraviolet light or visible light by irradiating transmissive radiation is employed. It is desired to bring the fluorescent screen close contact with both surfaces of the light-sensitive material comprising the emulsion of the present invention coated on both surfaces thereof and then to effect exposure.
- the transmissive radiation herein mentioned refers to an electromagnetic wave with high energy such as X-ray and gamma ray.
- the fluorescent screen includes a fluorescent screen comprising a fluorescent component composed mainly of calcium tungstate or a fluorescent screen composed mainly of a rare earth compound activated by terbium.
- Monodispersed grains of silver iodobromide containing 2.0 mole % of silver iodide with an average grain size of 0.2 ⁇ m were used as nuclei, and silver iodobromide containing 30 mole % of silver iodide was grown at pH 9.3 and pAg 7.5.
- monodispersed emulsion grains (A) with an average grain size of 1.50 ⁇ m, (B) with that of 1.20 ⁇ m, (C) with that of 0.70 ⁇ m and (D) with that of 0.41 ⁇ m, respectively, so that all the monodispersed emulsion grains obtained were silver iodobromide grains with an average silver iodide content of 2.3 mole.
- These emulsions were subjected to desalting to remove excessive salts according to the conventional coagulation method.
- (A), (B) and (C) were chemically ripened by adding 2.4 x 10 ⁇ 3 mole of ammonium thiocyanate per mole of silver, an optimum amount of chloroauric acid and hypo, and then stabilized by adding 2 x 10 ⁇ 2 mole of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
- the water-soluble dye was added in the emulsion coating solution for the side of the B surface.
- the respective coating solutions obtained were coated by two slide hopper type coaters simultaneously on both surfaces of a polyethylene terephthalate base with a thickness of 175 ⁇ m subjected to a subbing treatment so as to have a constitution as shown in Table 1, followed by drying for 2 minutes and 50 seconds, to obtain Samples No. 1 to No. 16.
- Silver amounts of both A and B surfaces were made 56 mg/dm2, respectively.
- sensitivities sA, sA', sB, sB' and Sw
- MTF MTF
- the additives used in the protective layer solution are shown below. An amount added is indicated as an amount per liter of the coating solution.
- the samples were developed by using an automatic processor KX-500 (trade name) and a developing solution XD-90 (trade name) at 35 °C for 30 sec, and fixed by a fixing solution XF, followed by washing and drying according to the conventional method.
- reciprocals of exposure dosages required for obtaining a density of base density + fog density + 1.0 were determined to obtain sensitivities.
- sA, sB, sA' and sB' they were measured by the method as mentioned above (as the flurescent screen, NR-160 (trade name, produced by KONICA CORPORATION) was used).
- MTF was a value at a space frequency of 2.0/mm.
- the covering power (C.P) was measured by the method as described above.
- MTF is elevated without lowering sensitivity to greatly contribute to diagnostic properties.
- Example 2 To three kinds of the emulsions obtained, the same emulsion additives as in Example 1, water-soluble dyes shown in Table 2 and lime-treated gelatin were added to prepare emulsion coating solutions shown below. The water-soluble dye was added in the emulsion coating solution for the side of the B surface.
- the samples were developed by using an automatic processor KX-500 and a developing solution XD-90 at 35 °C for 30 sec, and fixed by a fixing solution XF, followed by washing and drying according to a conventional method.
- reciprocals of exposure dosages required for obtaining a density of base density + fog density + 1.0 were determined to obtain sensitivities.
- sA, sB, sA' and sB' they were measured by the method as mentioned above (as the flurescent screen, KO-250 (trade name, produced by KONICA CORPORATION) was used).
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Disclosed is a light-sensitive silver halide photographic material comprising:
a support;
a first light-sensitive unit comprising a first light-sensitive layer and a first non-light-sensitive layer; and
a second light-sensitive unit comprising a second light-sensitive layer and a second non-light-sensitive layer,
the first light-sensitive unit being provided on one side of the support and the second light-sensitive unit being provided on the other side of the support,
wherein a sensitivity of the first light-sensitive unit when exposure is effected only from the one side (sA), a sensitivity of the second light-sensitive unit when exposure is effected only from the other side (sB) and a sensitivity of the first light-sensitive unit when exposure is effected only from the other side (sA') satisfy the following equations:
a support;
a first light-sensitive unit comprising a first light-sensitive layer and a first non-light-sensitive layer; and
a second light-sensitive unit comprising a second light-sensitive layer and a second non-light-sensitive layer,
the first light-sensitive unit being provided on one side of the support and the second light-sensitive unit being provided on the other side of the support,
wherein a sensitivity of the first light-sensitive unit when exposure is effected only from the one side (sA), a sensitivity of the second light-sensitive unit when exposure is effected only from the other side (sB) and a sensitivity of the first light-sensitive unit when exposure is effected only from the other side (sA') satisfy the following equations:
- (I) sA/sA' > 4.0
- (II) sA/sB = 1.5 to 20
Description
- This invention relates to a light-sensitive silver halide photographic material for medical use excellent in sensitivity and sharpness, and also improved in diagnostic properties.
- In recent years, in light-sensitive silver halide photographic materials, a higher level of photographic performances such as high sensitivity, excellent graininess, high sharpness and high covering power has been demanded. To cope with such demand, for example, various complicated technical means such as control of a crystal habit of a silver halide crystal itself, a grain size distribution or a distribution of iodine concentration in each grain have been studied and put to practical use.
- Particularly, in light-sensitive silver halide photographic materials for medical use, since a minute change in a morbid state should be found accurately to improve diagnostic properties, sharpness of images after development is considered to be extremely important. For example, Japanese Unexamined Patent Publications No. 28827/1975, No. 185038/1982 and No. 158430/1989 disclose improvements in sharpness by incorporating a water-soluble dye in a light-sensitive layer and/or a layer adjacent thereto. However, according to these methods of the prior art, both of sensitivity and sharpness cannot be improved simultaneously, and there involves a drawback that when sharpness is improved, sensitivity is lowered. Accordingly, development of a technique which can improve sharpness without lowering sensitivity and also improve diagnostic properties has been strongly demanded.
- Accordingly, an object of the present invention is to provide a light-sensitive silver halide photographic material for medical use improved in sharpness without impairing sensitivity and also improved in diagnostic properties. Other objects of the present invention will be apparent from the following description.
- The present inventors have studied intensively to improve sharpness, and consequently found that the above object can be accomplished by the method described below, to accomplish the present invention.
- That is, the object of the present invention can be accomplished by:
- (1) a light-sensitive silver halide photographic material comprising:
a support;
a first light-sensitive unit comprising a first light-sensitive layer and a first non-light-sensitive layer; and
a second light-sensitive unit comprising a second light-sensitive layer and a second non-light-sensitive layer,
said first light-sensitive unit being provided on one side of said support and said second light-sensitive unit being provided on the other side of said support,
wherein a sensitivity of said first light-sensitive unit when exposure is effected only from said one side (sA), a sensitivity of said second light-sensitive unit when exposure is effected only from said other side (sB) and a sensitivity of said first light-sensitive unit when exposure is effected only from said other side (sA') satisfy the following equations:- (I) sA/sA' > 4.0
- (II) sA/sB = 1.5 to 20
- (2) the light-sensitive silver halide photographic material described in (1), wherein a ratio of a covering power of the A surface to that of the B surface is 1 : 1.5 or more (that of the B surface is larger than that of the A surface), and
- (3) the light-sensitive silver halide photographic material described in (1), wherein at least one of the light-sensitive silver halide photographic emulsion layer and the hydrophilic colloidal layer at the B surface side contains at least one water-soluble dye.
- In the following, the present invention will be explained in more detail.
- In the present invention, a sensitivity of a light-sensitive silver halide photographic material refers to a value determined according to the following method.
-
- 1-1. Fluorescent screen to be used (which varies depending on a light-sensitive wavelength of a film used)
- (a) In the case of a light-sensitive material having a sensitivity to blue region (a regular light-sensitive material)
Fluorescent screen mainly composed of CaWO₄ (e.g. a series of NR's manufactured by Konica Corporation) - (b) In the case of a light-sensitive material having a sensitivity to green region (an ortho light-sensitive material)
Fluorescent screen mainly composed of Gd₂O₂S activated with Tb (e.g. a series of KO's manufactured by Konica Corporation)
- (a) In the case of a light-sensitive material having a sensitivity to blue region (a regular light-sensitive material)
- 1-2. X-ray irradiation conditions
- 1-3. Exposure method
- After a fluorescent screen is placed only on a back side of a cassette and a sample (film) is laminated thereon, exposure is effected through aluminum steps under the above conditions 1-2.
-
- As for samples after development, a sample exposed only from an A surface side is divided into two pieces. From one piece, a B surface is removed for measuring sA, and from the other piece, an A surface is removed for measuring sB'. Next, also from a sample exposed only from a B surface side, an A surface and a B surface are removed in the same manner for measuring sB and sA', respectively. For four kinds of samples obtained, characteristic curves are measured, and from the characteristic curves obtained, reciprocals of exposure dosages required for obtaining a density of base density + fog density + 1.0 are determined to obtain sA, sB, sA' and sB'.
- In the case of light-sensitive materials having sensitivities to red region and infrared region, an exposure method varies depending on each light-sensitive material.
- The A surface and the B surface of the light-sensitive silver halide photographic material according to the present invention have a sensitivity of sA/sA' > 4.0, preferably 4.5 or more, more preferably 5.0 to 15.0.
- Further, the sensitivity of the material is preferably sA/sB of 1.5 to 20, more preferably 2.5 to 10.
- As a method for making a sensitivity difference between an emulsion on an A surface and that of an emulsion on a B surface, various methods can be mentioned. As one of the methods to do so, at least one of the light-sensitive silver halide photographic emulsion layer and the hydrophilic colloidal layer at the B surface side contains at least one water-soluble dye.
- As another method, as a silver halide grain at the B surface side, one kind of grains with a small grain size is used, or when a plural kinds of grains are mixedly used, these grains are combinedly used so as to become an average grain size of the mixture small. Here, "small" means that the grain size of the B surface side is 70 to 80 % or less of that of the A surface side.
- As the water-soluble dye, those generally known in the art can be employed.
- In a preferred embodiment of the present invention, silver halide grains with a small grain size is used at the B surface side, and at least one of the above silver halide emulsion layer and the hydrophilic colloidal layer contains the dye as described above.
- Next, a covering power mentioned in the present invention is a photographic density obtained by a predetermined amount of silver, and defined as described below.
- Specifically, a covering power (C.P) is represented by the following formula:
- C.P
- (covering power) = D/S x 1,000
- S =
- Amount of silver (mg) per 100 dm² of one surface of light-sensitive material after development
- D =
- Density of one surface of the light-sensitive material after development
- When a ratio of the covering power of the A surface to that of the B surface of the light-sensitive silver halide photographic material according to the present invention is 1 : 1.5 or more (the covering power of the B surface is larger than that of the A surface), preferably 1 : 1.5 to 5.0, more preferably 1 : 1.5 to 2.0, the effect of the present invention can be exhibited favorably.
- In the following, the dye which is used preferably in the present invention will be explained in more detail.
- The dye which can be used in the present invention include, for example, arylidene dyes disclosed in U.K. Patents No. 584,609 and No. 1,210,252, U.S. Patents No. 2,538,008, No. 2,538,009, No. 2,688,541 and No. 4,420,555, styryl dyes disclosed in Japanese Patent Publications No. 3082/1953, No. 16594/1969 and No. 28898/1984, merocyanine dyes disclosed in U.S. Patents No. 3,486,897, No. 2,706,193, No. 3,260,601 and No. 4,035,190, cyanine dyes disclosed in U.S. Patents No. 2,843,486, No. 3,294,539 and No. 3,615,562, oxonol dyes disclosed in U.S. Patents No. 3,247,127, No. 3,469,985, No. 4,078,933, No. 2,533,472 and No. 3,379,533, azo dyes disclosed in U.S. Patent No. 3,671,254 and Japanese Unexamined Patent Publication No. 211043/1984 and azomethine dyes disclosed in U.K. Patents No. 750,031 and No. 2,014,598. Among them; preferred are dyes which can be decolored in a developing solution and a fixing solution containing a sulfite (e.g. arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes and oxonol dyes).
-
- As a layer in which the dye as described above is to be contained, any layer may be selected, but the dye may be contained in at least one layer of a light-sensitive emulsion layer and other hydrophilic colloidal layers at the side where said emulsion layer is coated (e.g. non-light-sensitive layers such as an intermediate layer, a protective layer, a subbing layer and a mordant layer) or may be contained by dispersing therein. Preferably, the dye may be contained in a silver halide emulsion layer or a layer nearer to a support than the silver halide emulsion layer or in both of these layers.
- The amount of the above dye to be added is preferably 0.2 mg/m² to 150 mg/m², more preferably 0.8 mg/m² to 50 mg/m².
- The dye can be introduced into a hydrophilic colloidal layer according to a conventional method. Specifically, the dye is prepared to be an aqueous solution having an appropriate concentration, and when an emulsion layer is colored, the aqueous solution of the dye may be added in a silver halide emulsion or an aqueous hydrophilic colloidal solution before coating, and then coated.
- The dye according to the present invention may be carried within a layer by using a mordant.
- For example, as a mordant which can make a dye nondiffusible by bonding at least one dye as described above to a mordant, compounds disclosed in, for example, U.S. Patents No. 2,548,564, No. 2,675,316, No. 2,795,519, No. 2,839,401, No. 2,882,156, No. 3,048,487, No. 3,184,309, No. 3,444,138, No. 3,445,231, No. 3,706,563, No. 3,709,690 and No. 3,788,855 can be preferably used.
-
- In the present invention, as a nonionic surfactant to be used when employed as a mordant layer, nonionic surfactants known in the art may be used.
-
- The hydrophilic colloidal layer mentioned in the present invention refers to a hydrophilic layer provided in layers of a light-sensitive silver halide photographic material, and refers to various layers which contain a binder component such as gelatin and are necessary for a light-sensitive material for photography such as a silver halide emulsion layer, a protective layer, an intermediate layer, an antihalation layer, a filter layer, a development controlling layer, an UV absorbing layer and a prime-coating layer.
- In the most preferred embodiment of the present invention, on one surface of a polyethylene terephthalate film support of which both surfaces have been subjected to a subbing treatment, a high sensitivity silver halide emulsion layer is coated as an A surface, and a protective layer containing gelatin as a binder component is provided thereon.
- Next, on the opposite surface thereof, a low sensitivity silver halide emulsion layer having a sensitivity different from that of the A surface is coated as a B surface. In said emulsion layer, the water-soluble dye according to the present invention may be added and contained, and further, a hydrophilic colloidal layer (e.g. a gelatin layer containing a dye or a mordant layer on which a dye is carried) may be provided above or under said emulsion layer.
- 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 silver iodobromide is preferred since a light-sensitive material having a particularly high sensitivity can be obtained.
- The silver halide grains in the photographic emulsion may have any shape such as cube, octahedron and tetradecahedron which grow in an isotropic manner, or polyhedral crystal such as sphere and twin having defects in phases or a mixture or complex thereof. The silver halide grains may have a grain size of from 0.1 µm (fine particles) or less to 20 µm (big particles).
- The emulsion to be used in the light-sensitive silver halide photographic material of the present invention can be prepared according to the known method. For example, the emulsion can be prepared according to "1. Emulsion Preparing Method (Emulsion Preparation and types)" disclosed at pp. 22 to 23 of Research Disclosure (RD) No. 17643 (December, 1978) and the method disclosed at p. 648 of RD No. 18716 (November, 1979).
- As a preferred embodiment of the present invention, a monodispersed emulsion in which silver iodide exists locally internally of its grain can be mentioned. The monodispersed emulsion herein mentioned refers to silver halide grains wherein, for example, when an average grain diameter is measured according to the conventional method, at least 95 % of the grains in terms of the grain number or weight have a grain diameter preferably within ± 40 %, more preferably within ± 30 % of the average grain size. A grain size distribution of the silver halide may be a narrow distribution as in the case of a monodispersed emulsion or a wide distribution as in the case of a polydispersed emulsion.
- Crystalline structure of the silver halide may comprise different silver halide compositions at an inner portion and an outer portion.
- As a preferred embodiment of the present invention, the emulsion is a core/shell type monodispersed emulsion having a clearly two-layered structure comprising a core portion with a high iodine content and a shell layer with a low iodine content.
- An amount of silver iodide in the portion with a high iodine content of the present invention is 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, Journal of Photographic Science, vol. 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, and U.S. Patents No. 3,574,628 and No. 3,655,394.
- As the monodispersed emulsion as described above, particularly preferred is an emulsion in which a seed crystal is used as a growth nucleus and grains are grown by supplying a silver ion and a halide ion. Further, 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.
- The silver halide emulsion to be used in the present invention may be a tabular grain having an aspect ratio of 5 or more.
- Such a tabular grain have advantages that improvement in spectral sensitizing efficiency and improvement in graininess and sharpness of images can be accomplished, and it can be prepared according to the methods disclosed in, for example, U.K. Patent No. 2,112,157, and U.S. Patents No. 4,439,520, No. 4,433,048, No. 4,414,310 and No. 4,434,226.
- The above emulsion may be any emulsion of 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. In the emulsion, during physical ripening or preparation of grains, cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof and iron salt or complex salt thereof may be used. For removing soluble salts, the emulsion may be subjected to a noodle washing method, a flocculation sedimentation method or an ultra-filtration method. As a preferred washing method, there may be included, as particularly preferred desalting methods, a method of using an aromatic hydrocarbon type aldehyde resin containing sulfo group as disclosed in Japanese Patent Publication No. 16086/1960 and a method of using exemplary compounds G3 and G8 of a coagulating polymeric agent as disclosed in Japanese Unexamined Patent Publication No. 158644/1988.
- In the emulsion according to the present invention, in the step of before and after the step of physical ripening or chemical ripening, various additives for photography can be used. As the additives known in the art, compounds disclosed in, for example, Research Disclosure No. 17643 (December, 1978) and Research Disclosure No. 18716 (November, 1979) are included. Kinds of the compounds disclosed in these two Research Disclosures and pages are shown below.
- As a support which can be used in the light-sensitive material according to the present invention, those disclosed on p. 28 of RD No. 17643 and in the left column of p. 647 of RD No. 18716 can be mentioned.
- A suitable support is a plastic film. Generally, for enhancing adhesiveness of the support to a coating layer, 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 ray irradiation. On one surface or both surfaces of the support thus treated, the emulsion according to the present invention can be coated.
- The present invention can be applied to all light-sensitive silver halide photographic materials, but it is particularly suitable for high sensitivity black and white light-sensitive materials.
- When the present invention is applied to X-ray radiography for medical use, for example, a fluorescent screen composed mainly of a fluorescent substance which emits near ultraviolet light or visible light by irradiating transmissive radiation is employed. It is desired to bring the fluorescent screen close contact with both surfaces of the light-sensitive material comprising the emulsion of the present invention coated on both surfaces thereof and then to effect exposure.
- The transmissive radiation herein mentioned refers to an electromagnetic wave with high energy such as X-ray and gamma ray.
- The fluorescent screen includes a fluorescent screen comprising a fluorescent component composed mainly of calcium tungstate or a fluorescent screen composed mainly of a rare earth compound activated by terbium.
- In the following, the present invention is described by referring to Examples. As a matter of course, the present invention is not limited by Examples as described below at all.
- Monodispersed grains of silver iodobromide containing 2.0 mole % of silver iodide with an average grain size of 0.2 µm were used as nuclei, and silver iodobromide containing 30 mole % of silver iodide was grown at pH 9.3 and pAg 7.5. Subsequently, at pH 7.8 and pAg 8.9, equimolar amounts of potassium bromide and silver nitrate were added to prepare monodispersed emulsion grains (A) with an average grain size of 1.50 µm, (B) with that of 1.20 µm, (C) with that of 0.70 µm and (D) with that of 0.41 µm, respectively, so that all the monodispersed emulsion grains obtained were silver iodobromide grains with an average silver iodide content of 2.3 mole. These emulsions were subjected to desalting to remove excessive salts according to the conventional coagulation method. Specifically, to the emulsions maintained at 40 °C were added a formalin condensate of sodium naphthalenesulfonate and an aqueous solution of magnesium sulfate to effect coagulation. After a supernatant liquid was removed, pure water up to 40 °C was added and then an aqueous solution of magnesium sulfate was added again to effect coagulation, followed by removing a supernatant liquid.
- Among the emulsions obtained, (A), (B) and (C) were chemically ripened by adding 2.4 x 10⁻³ mole of ammonium thiocyanate per mole of silver, an optimum amount of chloroauric acid and hypo, and then stabilized by adding 2 x 10⁻² mole of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
- To the three kinds of the emulsions obtained were added emulsion additives described below, water-soluble dyes shown in Table 1 and lime-treated gelatin to prepare emulsion coating solutions shown below.
- The water-soluble dye was added in the emulsion coating solution for the side of the B surface.
- Coating solution 1:
- a solution in which a mixing ratio of
(A):(B):(C) is 20.0:40.0:40.0 - Coating solution 2:
- a solution in which a mixing ratio of
(A):(B) is 33.3:66.7 - Coating solution 3:
- a solution comprising only (C)
- Coating solution 4:
- a solution in which a mixing ratio of
(A):(B) is 40.0:60.0 - Coating solution 5:
- a solution in which a mixing ratio of
(A):(B) is 20.0:80.0 - Further, a protective film coating solution having a composition shown below was prepared.
- The respective coating solutions obtained were coated by two slide hopper type coaters simultaneously on both surfaces of a polyethylene terephthalate base with a thickness of 175 µm subjected to a subbing treatment so as to have a constitution as shown in Table 1, followed by drying for 2 minutes and 50 seconds, to obtain Samples No. 1 to No. 16.
- Silver amounts of both A and B surfaces were made 56 mg/dm², respectively.
- For the samples obtained, according to a method as described below, sensitivities (sA, sA', sB, sB' and Sw) and MTF were measured, and diagnostic properties were evaluated.
- The results are shown in Table 1. As a fluorescent screen, NR-160 (manufactured by Konica Corporation) was employed.
-
-
- The measurement and evaluation were conducted according to the following methods.
- The samples were sandwiched between 2 sheets of fluorescent screen NR-160 (trade name, produced by KONICA CORPORATION) and exposed through aluminum steps under the following conditions:
Voltage in tube: 80 Kvp
Current in tube: 100 mA
Irradiation time: 50 msec - Then, the samples were developed by using an automatic processor KX-500 (trade name) and a developing solution XD-90 (trade name) at 35 °C for 30 sec, and fixed by a fixing solution XF, followed by washing and drying according to the conventional method. For the samples obtained, reciprocals of exposure dosages required for obtaining a density of base density + fog density + 1.0 were determined to obtain sensitivities.
- As for sA, sB, sA' and sB', they were measured by the method as mentioned above (as the flurescent screen, NR-160 (trade name, produced by KONICA CORPORATION) was used).
- For the respective samples, each rectangular wave chart was photographed, and MTF was determined according to a contrast method. MTF was a value at a space frequency of 2.0/mm.
- By using each sample, a chest phantom (manufactured by Kyoto Kagaku K.K.) was photographed, and development was conducted according to the same conditions as in the measurement of sensitivity. Overall evaluation was made by observation with eyes, and the results are represented by 5 ranks. In the ranks 5 to 3, there is no problem in practical use, but in the ranks 2 to 1, samples are of no practical use.
- The covering power (C.P) was measured by the method as described above.
-
- As clearly seen from Table 1, it can be understood that according to the present invention, MTF is elevated without lowering sensitivity to greatly contribute to diagnostic properties.
- To the above emulsions (B), (C) and (D) were added spectral sensitizing dyes A and B shown below at a weight ratio of 200:1 in a total amount of 800 mg per mole of silver halide, respectively. Subsequently, the mixtures were chemically ripened by using 3.6 x 10⁻³ mole of ammonium thiocyanate per mole of silver, an optimum amount of chloroauric acid and hypo. Fifteen minutes before completion of the reaction, 200 mg of potassium iodide per mole of silver was added, and then 2 x 10⁻² mole of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to effect stabilization.
-
-
- To three kinds of the emulsions obtained, the same emulsion additives as in Example 1, water-soluble dyes shown in Table 2 and lime-treated gelatin were added to prepare emulsion coating solutions shown below. The water-soluble dye was added in the emulsion coating solution for the side of the B surface.
- Coating solution 6:
- a solution in which a mixing ratio of
(B):(C):(D) is 25.0:35.0:40.0 - Coating solution 7:
- a solution in which a mixing ratio of
(B):(C) is 41.7:58.3 - Coating solution 8:
- a solution comprising only (D)
- Coating solution 9:
- a solution in which a mixing ratio of
(B):(C) is 50.0:50.0 - Coating solution 10:
- a solution in which a mixing ratio of
(C):(D) is 20.0:80.0 - The coating solutions obtained were coated on a support and dried in the same manner as in Example 1 to obtain Samples No. 1 to No. 16.
- For the samples obtained, sensitivity and MTF were measured and diagnostic properties were evaluated in the same manner as in Example 1. The results are shown in Table 2. Sensitivity (Sw) in Table 2 was measured according to the following method.
- The samples were sandwiched between 2 sheets of fluorescent screen KO-250 and exposed through aluminum steps under the following conditions:
Voltage in tube: 80 Kvp
Current in tube: 100 mA
Irradiation time: 50 msec - Then, the samples were developed by using an automatic processor KX-500 and a developing solution XD-90 at 35 °C for 30 sec, and fixed by a fixing solution XF, followed by washing and drying according to a conventional method. For the samples obtained, reciprocals of exposure dosages required for obtaining a density of base density + fog density + 1.0 were determined to obtain sensitivities.
- As for sA, sB, sA' and sB', they were measured by the method as mentioned above (as the flurescent screen, KO-250 (trade name, produced by KONICA CORPORATION) was used).
-
- As clearly seen from Table 2, also in a system subjected to ortho sensitization, the effect of the present invention was exhibited markedly similarly as in Example 1.
- According to the present invention, sharpness could be improved without lowering sensitivity. The effect of the present invention thus obtained was significant in a light-sensitive silver halide photographic material for medical use for improving diagnostic properties.
wherein the density (D) is a density obtained by measuring by means of a densitometer PDA-65 (trade name, manufactured by Konica Corporation) the light-sensitive material which has been exposed by using an incandescent lamp of 100 W at a voltage of 50 V for 3 seconds and developed by using XD-90 and XF (trade name, each available from Konica Corporation) and an automatic processor KX-500 (trade name, manufactured by Konica Corporation) at a developing temperature of 35 °C.
Claims (10)
- A light-sensitive silver halide photographic material comprising:
a support;
a first light-sensitive unit comprising a first light-sensitive layer and a first non-light-sensitive layer; and
a second light-sensitive unit comprising a second light-sensitive layer and a second non-light-sensitive layer,
said first light-sensitive unit being provided on one side of said support and said second light-sensitive unit being provided on the other side of said support,
wherein a sensitivity of said first light-sensitive unit when exposure is effected only from said one side (sA), a sensitivity of said second light-sensitive unit when exposure is effected only from said other side (sB) and a sensitivity of said first light-sensitive unit when exposure is effected only from said other side (sA') satisfy the following equations: - The material of Claim 1 wherein said sA/sA' is 4.5 or more.
- The material of Claim 2 wherein said sA/sA' is 5.0 or more.
- The material of Claim 1 wherein said sA/sB is 2.5 to 10.
- The material of Claim 2 wherein the ratio is 1 : 1.5 to 5.0.
- The material of Claim 5 wherein the ratio is 1 : 1.5 to 2.0.
- The material of Claim 1 wherein at least one of the light-sensitive silver halide photographic emulsion layer and the hydrophilic colloidal layer at the B surface side contains at least one water-soluble dye.
- The material of Claim 1 wherein silver halide grains with a small grain size are used at the B surface side.
- The material of Claim 1 wherein a constitution rate of fine silver halide grains used at the B surface side is made larger.
- The material of Claim 1 wherein silver halide grains with a small grain size is used at the B surface side and a water-soluble dye is added to at least one of the above silver halide emulsion layer and the hydrophilic colloidal layer.
Applications Claiming Priority (2)
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JP2949/90 | 1990-01-10 | ||
JP294990 | 1990-01-10 |
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EP0520409A1 (en) * | 1991-06-26 | 1992-12-30 | Konica Corporation | Light-sensitive silver halide photographic material image quality- and gradation-adaptable to photographing purposes and image forming method therefor |
WO1993009468A1 (en) * | 1991-11-07 | 1993-05-13 | E.I. Du Pont De Nemours And Company | Radiographic materials with increased uv sensitivity |
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EP0470733A1 (en) * | 1990-08-08 | 1992-02-12 | Konica Corporation | Light-sensitive silver halide photographic material |
US5238795A (en) * | 1990-08-08 | 1993-08-24 | Konica Corporation | Light-sensitive silver halide photographic material |
US5470700A (en) * | 1990-10-12 | 1995-11-28 | Konica Corporation | Light-sensitive silver halide X-ray photographic material containing a mixture of tabular grains |
EP0520409A1 (en) * | 1991-06-26 | 1992-12-30 | Konica Corporation | Light-sensitive silver halide photographic material image quality- and gradation-adaptable to photographing purposes and image forming method therefor |
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 |
US5399470A (en) * | 1991-08-16 | 1995-03-21 | Eastman Kodak Company | Minimal crossover radiographic elements and assemblies adapted for flesh and bone imaging |
WO1993009468A1 (en) * | 1991-11-07 | 1993-05-13 | E.I. Du Pont De Nemours And Company | Radiographic materials with increased uv sensitivity |
US5380636A (en) * | 1992-10-05 | 1995-01-10 | Minnesota Mining & Manufacturing Company | Multicontrast radiographic film-screen assembly |
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