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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

• This invention relates to a silver halide light-sensitive color photographic material, and more particularly to a silver halide light-sensitive color photographic material which is excellent in sharpness of the dye image formed.
• a silver halide light-sensitive color photographic material comprises a plurality of light-sensitive silver halide emulsion layers uniformly applied on a support made of for example cellulose triacetate, polyethylene terephthalate or the like. Each of these emulsion layers has a dry film thickness of several microns and exhibits different color sensitivity.
• These light-sensitive silver halide emulsion layers contain many silver halide grains which have a grain size approximately corresponding to the wavelength of visible ray and exhibit various crystal habits, and which are dispersed in a hydrophilic colloid exhibiting a refractive index smaller than that of a silver halide, such as gelatin.
• a visible ray is applied perpendicularly to the surface of a light-sensitive silver halide emulsion layer of this type, the visible ray is scattered by the silver halide grains in the layer.
• This phenomenon is interpreted to occur because the grain size is approximately equal to the wavelength of the visible ray and because the refractive indices of the grains and the binder are different from each other.
• the degree of the scattering differs according to the number of grains contained in the unit volume of the light-sensitive silver halide emulsion layer, grain size, grain size distribution, difference between the refractive indices of the silver halide grains and the binder.
• the film thickness of the silver halide emulsion layer is minimized by reducing the proportion of silver halide grains with respect to gelatin in the light-sensitive silver halide emulsion layer, reducing the average crystal size of the silver halide grains in the light-sensitive silver halide emulsion layer used as the uppermost layer, or by decreasing the amount of the binder used in the light-sensitive silver halide emulsion.
• these methods have serious drawbacks.
• sensitivity of an emulsion layer generally deteriorates when the grain sizes of silver halide grains are reduced. Further, if the amount of the binder contained in the emulsion layer is substantially reduced, the amount of the coupler which can be added to the emulsion layer also decreases, resulting in a low sensitivity of the emulsion.
• the uppermost layer of the green-sensitive silver halide emulsion is also sensitive to the blue light region which is the sensitive region intrinsic to the silver halide emulsion. This fact is unfavorable to the green-sensitive silver halide. Normally, it is desirable that only the blue-sensitive silver halide emulsion layer be sensitive to blue light. This phenomenon of the green-sensitive silver halide emulsion results in fatal defects in the color reproduction of the color photosensitive material.
• An object of the present invention is to provide a silver halide light-sensitive color photographic material exhibiting an improved sharpness of the dye image formed therein.
• the present invention relates to a silver halide light-sensitive color photographic material comprising blue-sensitive, green-sensitive, and red-sensitive negative type light-sensitive silver halide emulsion layers provided on a support, characterized in that at least 80% of silver halide grains contained in the light-sensitive silver halide emulsion layer farthest from said support or in the green-sensitive silver halide emulsion layer are constituted by regular-crystal silver halide grains.
• the silver halide light-sensitive color photographic material in accordance with the present invention exhibits an improved sharpness of the dye image formed therein.
• negative type light-sensitive silver halide emulsion as used herein has a meaning opposite to the direct positive type silver halide emulsion.
• the negative type silver halide emulsion in the present invention means a silver halide emulsion which has the sensitive nuclei at the surfaces of the silver halide grains and which yields blackened silver in proportion to the lightness of the object when developed with a surface developing solution after the exposure.
• the regular-crystal silver halide grains used in the silver halide light-sensitive photographic material in accordance with the present invention means silver halide crystal grains having a regular form, in which the outer crystal habit essentially consists only of [100] face and/or [111] face. Thus it is used as a concept opposite to the twinned crystal.
• Typical regular-crystal silver halide grains in the present invention are those having a regular cubic, octahedral or tetradecahedral form.
• the regular-crystal silver halide grains in accordance with the present invention at least 80% of all silver halide grains contained therein are constituted by the regular-crystal silver halide grains defined above.
• At least 80% of the silver halide grains contained in the light-sensitive silver halide emulsion layer located at the position farthest from the support are constituted by the regular-crystal silver halide grains defined above.
• At least 80% of the silver halide grains contained in the light-sensitive silver halide emulsion layer, which is sensitive to green light are constituted by the above-mentioned regular-crystal silver halide grains.
• the above-mentioned green-sensitive silver halide emulsion layer is not located at the position farthest from the support, it is further preferable that at least 80% of the total silver halide grains contained in each of said green-sensitive silver halide emulsion layer and said farthest light-sensitive silver halide emulsion layer are constituted by the above-mentioned regular-crystal silver halide grains.
• At least 80% of the silver halide grains contained in all light-sensitive silver halide emulsion layers constituting the silver halide light-sensitive color photographic material in accordance with the present invention are constituted by the regular-crystal silver halide grains.
• the silver halide grains used in the silver halide light-sensitive photographic material in accordance with the present invention may be prepared by the acid process, neutral process or ammonia process.
• ions of noble metals such as Ir, Rh, Pt and Au may be added in the course of the grain growth so as to include them in the interiors of the grains, or reduction sensitization nuclei may be formed in the interiors of the grains by using a low pAg atmosphere or an appropriate reducing agent.
• the silver halide emulsions used in the present invention may be adjusted to a pAg value or an ion concentration suitable for chemical sensitization by using an appropriate method after the growth of the silver halide grains is finished.
• an appropriate method for example, the aggregation method and the noodle water-washing method as described in Research Disclosure No. 17643 may be used.
• the regular-crystal silver halide emulsion may be used without changing its crystal size distribution, or two or more regular-crystal emulsions having different average crystal sizes may be blended together to obtain a desired gradient of characteristic curve at an arbitrary point of time after the formation of grains. It is preferable, however, to blend them after the chemical ripening.
• the light-sensitive silver halide emulsion layer located at the position farthest from the support, or the green-sensitive silver halide emulsion layer in the silver halide light-sensitive color photographic material in accordance with the present invention may contain silver halide grains other than the regular crystals, for example twinned- crystal silver halide grains, in an amount not exceeding 20% of the total grains contained in the layer.
• the content of silver halide grains other than the regular crystals be limited to 10% or less, and it is more preferable that the layer is substantially free from silver halide grains other than the regular crystals.
• the cubic, octahedral and tetradecahedral crystal grains may be used alone or two or more thereof may be mixed in any proportions.
• the proportions of the octahedral grains and/or tetradecahedral grains be larger than that of the cubic grains, and it is more preferable that the crystal grains be constituted only by octahedral grains and/or tetradecahedral grains.
• composition of the silver halides in the silver halide emulsions there is no limitation regarding the composition of the silver halides in the silver halide emulsions, and a composition usually employed may be used.
• a composition usually employed may be used in a negative emulsion for general photography.
• a composition containing silver bromide as the main constituent and optionally 12 mol % or less of silver iodide and 10 mol % or less of silver chloride is preferably used.
• silver chlorobromide emulsions, silver chloroiodobromide emulsions or the like containing silver chlorobromide or silver chloride as the main constituent may be used.
• each emulsion be chemically sensitized in a manner suitable thereto.
• the chemical sensitization may be conducted by a known method such as sulfur sensitization, gold sensitization, selenium sensitization, and reduction sensitization. Two or more of these sensitization methods may be combined.
• the reaction rate differs according to the crystal size of the silver halide, and the respective emulsions cannot necessarily exhibit their maximum reaction rates if they are sensitized by the same method or after blended together instead of being individually sensitized.
• the sulfur sensitization may be conducted by using for example sodium thiosulfate, thiourea, allyl thiourea or the like.
• the gold sensitization can be conducted by using for example sodium chloroaurate, potassium aurothio- cyanate or the like. It is also possible to conduct gold-sulfur chemical sensitization by using at least one sulfur sensitizing agent and at least one gold sensitizing agent listed above. In this case, ammonium thiocyanate or the like may further be added.
• the selenium sensitization method may also be applied for the silver halide emulsions used in the present invention.
• methods using selenourea, N,N'-dimethylselenourea or the like, as described for example in U.S. Patent Nos. 1,574,944 and 3,591,385, Japanese Patent Publication Nos. 13849/1968 and 15748/1969 may be used.
• reduction sensitization according to the conventional procedure. This can be done for example by the ripening in a low pAg atmosphere or by using an appropriate reducing agent or an electromagnetic wave such as light and y-ray.
• the two or more emulsions having different average crystal sizes may be applied as separate layers on the support or may be applied as one layer after mixing.
• the support used in this case may be of any known material for example a polyester film such as polyethylene terephthalate, a polyamide film, a polycarbonate film, a styrene film, baryta paper, or paper coated with a synthetic polymer.
• the silver halide light-sensitive color photographic material in accordance with the present invention is particularly suitable as the negative type silver halide color photographic material for the purpose of taking a picture, which is required to exhibit a high sensitivity and a high image quality.
• the hydrophilic colloid used to disperse the silver halide grains therein in accordance with the present invention is most preferably gelatin.
• gelatin derivatives other natural hydrophilic colloids such as albumin, casein, agar, gum arabic, alginic acid and its derivatives e.g.
• cellulose derivatives such as cellulose ethers, partially hydrolyzed cellulose acetate and carboxymethyl cellulose
• synthetic hydrophilic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, homopolymers and copolymers of acrylic acid and methacrylic acid or their derivatives e.g. esters, amides and nitriles thereof, and vinyl polymers e.g. vinyl ethers and vinyl esters.
• the silver halide emulsions used in the silver halide light-sensitive photographic material in accordance with the present invention may also contain stabilizers and fog restrainers as described for example in U.S. Patent Nos. 2,444,607, 2,716,062, 3,512,982, and 3,342,596, German Patent Nos. 1,189,380, 205,862 and 211,841, Japanese Patent Publication Nos. 4183/1968 and 2825/1964, and Japanese Provisional Patent Publication Nos. 22626/1975 and 25218/1975.
• Examples of particularly preferable compounds used for this purpose are 5,6-trimethylene-7-hydroxy-8-triazolo(l,5-a)pyrimidine, 5,6-tetramethylene-7-hydroxy-8-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-8-triazolo(l,5-a)pyrimidine, 7-hydroxy-8-triazolo(1,5-a)pyrimidine, gallates such as isoamyl gallate, dodecyl gallate, propyl gallate and sodium gallate, mercaptans such as 1-phenyl-5-mercaptotetrazole and 2-mercaptobenzothiazole, benzotriazoles such as 5-bromobenzotriazole and 4-methylbenzotriazole, and benzoimidazoles such as 6-nitrobenzo- imidazole.
• the silver halide emulsions in the present invention may be subjected to the spectral sensitization by using known spectral sensitizing dyes such as cyanine dye and merocyanine dye according to the conventional procedure.
• spectral sensitizing dyes such as cyanine dye and merocyanine dye according to the conventional procedure.
• sensitizing dyes for the regular region, it is possible to use sensitizing dyes as described in Japanese Provisional Patent Publication Nos. 2756/1980 and 14743/1 980 .
• the sensitizing dyes as described in Japanese Provisional Patent Publication Nos. 56425/1973 and 31228/1976, and Japanese Patent Publication No. 25379/1972 may be used. These dyes may be used alone or in combination with one another.
• the spectral sensitization for the long wavelength range can be conducted by using a cyanine dye having a longer methine group as described in Japanese Provisional Patent Publication No. 126140/1976. It is also possible to conduct the supersensitization by use of a combination of dyes.
• the coating composition for the silver halide photosensitive material in accordance with the present invention may contain photographic hardeners usually used in this field such as for example aldehydes, aziridines as described for example in PB Report 19,921, U.S. Patent Nos. 2,950,197, 2,964,404, 2,983,611 and 3,271,175, Japanese Patent Publication No. 40898/1971 and Japanese Provisional Patent Publication No. 91315/1975, isoxazoles as described e.g. in U.S. Patent No. 331,609, epoxy compounds as described e.g. in U.S. Patent No. 3,047,394, West German Patent No. 1,085,663, British Patent No. 1,033,518 and Japanese Patent Publication No.
• photographic hardeners usually used in this field such as for example aldehydes, aziridines as described for example in PB Report 19,921, U.S. Patent Nos. 2,950,197, 2,964,404, 2,983,611 and 3,271,175, Japanese Patent Publication No. 4
• the coating composition in accordance with the present invention may contain thickening agents as described e.g. in U.S. Patent No. 3,167,410 and Belgian Patent No. 558,143, gelatin plasticizers such as polyols as described e.g. in U.S. Patent No. 2,960,404, Japanese Patent Publication 4939/1968 and Japanese Provisional Patent Publication No. 63715/1973, and latices as described e.g. in U.S. Patent No. 766,976, French Patent No. 1,395,544 and Japanese Patent Publication No. 43125/1973, and matting agents as described e.g. in British Patent No. 1,221,980.
• composition for the silver halide light-sensitive photographic material in accordance with the present invention may contain a desired auxiliary such as saponin or a sulfosuccinic acid surface active agent as described e.g. in British Patent No. 548,532 and Japanese Provisional Patent Publication No. 46733/1974 or an anionic surface active agent as described e.g. in Japanese Patent Publication No. 18156/1968, U.S. Patent No. 3,514,293, French Patent No. 2,025,688 and Japanese Patent Publication No. 10247/1968.
• dyes may be used in the layer which is below the emulsion layers in accordance with the present invention and which contacts the support. Further, for the purpose of improving image sharpness or reducing fog due to safelight, dyes may be added to the protective layer and/or the emulsion layers in accordance with the present invention and/or the non-photosensitive layer contacting the emulsion layer in accordance with the present invention. For this purpose, any of dyes known for this purpose may be used.
• the emulsions in accordance with the present inven-. tion may be applied to the color light-sensitive material by using the technology and materials which are usually used for general color light-sensitive materials and the false color light-sensitive materials as described in Imaging No. 18-19 (1976).
• a combination of cyan, magenta and yellow couplers may be added to the emulsions in accordance with the present invention, whose red, green and blue sensitivities have been adjusted.
• couplers examples include open-chain methylene series yellow couplers, pyrazolone series magenta couplers, phenol or naphthol series cyan couplers. These couplers may be used in combination with colored couplers for auto masking, e.g.
• couplers having a split-off group, which has an azo lid as the bonding lid, bonded to the active point of the coupler; osazone compounds; development diffusing dye-releasing couplers; development inhibitor- releasing compounds, which release a development inhibitor by the reaction with the oxidized product of an aromatic primary amine developing agent and which embrace both DIR couplers forming a color by reacting with the oxidized product of the aromatic primary amine developing agent and DIR substances forming a colorless compound.
• These couplers may be incorporated into the silver halide color light-sensitive photographic material according to various procedures known for such couplers.
• the silver halide light-sensitive photographic material in accordance with the present invention can be developed by the known methods usually employed.
• the bleach developing solution may be a usually employed developing solution containing e.g. hydroquinone, l-phenyl-3-pyrazolidone, N-methyl-p-aminophenol or p-phenylenediamine alone or in the form of a combination of two or more thereof. It is also possible to use other additives usually employed.
• the light-sensitive material is used for color photographic purpose, it can be color- developed by usual color development method.
• a developing solution containing an aldehyde hardener can also be used for the silver halide light-sensitive material in accordance with the present invention.
• developing solution known in the field of photography containing dialdehydes such as maleic dialdehyde, glutaric dialdehyde or their salts with sodium bisulfite.
• An aqueous ammoniacal silver nitrate solution and an aqueous alkali halide solution were admixed with an aqueous gelatin solution containing alkali halides at 50° C. over 15 minutes according to the usual double jet mixing method.
• a silver iodobromide emulsion having an average crystal size of 0.65 n and a standard deviation of 0.21 p and containing 5 mol % of silver iodide with the content of twinned crystals being 30%, was prepared.
• aqueous ammoniacal silver nitrate solution and an aqueous alkali halide solution were admixed with an aqueous gelatin solution containing alkali halides at 40° C. over 83 minutes by maintaining the pAg value at 8.6 according to the pAg-controlled double jet mixing method.
• a silver iodobromide emulsion having an average crystal size of 0.65 p and a standard deviation of 0.154 ⁇ and containing 5 mol % of essentially cubic silver iodide, with the content of twinned crystals being 12%, was obtained.
• aqueous ammoniacal silver nitrate solution and an aqueous alkali halide solution were precipitated in an aqueous gelatin solution containing alkali halides at 40° C. over 105 minutes by maintaining the pAg value at 9.85 according to the pAg-controlled double jet mixing method.
• a silver iodobromide emulsion having an average grain size of 0.68 ⁇ and a standard deviation of 0.142 p and containing 5 mol % of essentially octahedral silver iodide, with the content of twinned crystals being 12%, was obtained.
• aqueous ammoniacal silver nitrate solution and an aqueous alkali halide solution were admixed with an aqueous gelatin solution containing alkali halides at 40° C. over 60 minutes by maintaining the pAg value at 9.5 and later 20 minutes the pAg value at 10.4 according to the pAg-controlled double jet mixing method.
• a silver iodobromide emulsion having an average crystal size of 0.65 ⁇ and a standard deviation of 0.157 p and containing 5 mol % of essentially tetradecahedral silver iodide, with the content of twinned crystals being 12%, was obtained.
• the support was a under-coated cellulose triacetate film. In this way, specimens 1 - 19 were prepared.
• An aqueous gelatin solution containing black colloidal silver dispersed therein was applied so as to obtain a dry film thickness of 2.0 ⁇ .
• the primitive emulsion 1 was chemically sensitized with a gold sensitizing agent and a sulfur sensitizing agent. Further, as the sensitizing dyes, anhydrous 9-ethyl-3,3'-di-(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide and anhydrous 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)thiacarbo- cyanine hydroxide were added.
• the primitive emulsion 1 was chemically sensitized with a gold sensitizing agent and a sulfur sensitizing agent. Further, as the sensitizing dyes, anhydrous 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl) oxacarbocyanine hydroxide, anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine and anhydrous 9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5',6'-dibenzooxacarbocyanine hydroxide were added.
• An aqueous gelatin solution was applied so as to obtain a dry film thickness of 1.0 ⁇ .
• the primitive emulsion 1 was chemically sensitized with a gold sensitizing agent and a sulfur sensitizing agent. Further, 4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added. Thereafter, the dispersion (Y-l) described later and 1,2-bisvinylsulfonylethane were added to prepare a blue-sensitive silver halide emulsion. The emulsion thus prepared was applied to obtain a dry film thickness of 5.0 ⁇ .
• Layer 1 Antihalation layer (same as the layer 1 of specimen 1)
• the primitive emulsion 2 was chemically sensitized with gold and sulfur sensitizing agents, it was treated in the same way as the layer 2 of the specimen 1 and then applied.
• Layers 3, 4, 5, 6, 7 and 8 were prepared in the same ways as the layers, 3, 4, 5, 6, 7 and 8 of the specimen 1 respectively, and then applied.
• the specimen 3 was prepared by sequentially applying the layers of the specimen 1 on a cellulose triacetate support in the same way as the specimen 1, except that the layer 4 (green-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 2 with gold and sulfur sensitizing agents and then treating it in the same manner as the layer 4 of the specimen 1.
• the specimen 4 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1, except that the same emulsion as the layer 2 of the specimen 3 was applied as the layer 2 (red-sensitive emulsion layer), and the same emulsion as the layer 4 of the specimen 3 was applied as the layer 4 (green-sensitive emulsion layer).
• the specimen 5 was prepared by sequentially applying the layers of the specimen 1 on a cellulose triacetate support in the same way as the specimen 1, except that the layer 7 (blue-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 2 with gold and sulfur sensitizing agents and then treating it in the same manner as the layer 7 of the specimen 1.
• the layer 7 blue-sensitive emulsion layer
• the specimen 6 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1, except that the same emulsion as the layer 4 of the specimen 3 was applied as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 5 was applied as the layer 7 (blue-sensitive emulsion layer).
• the specimen 7 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1, except that the same emulsion as the layer 2 of the specimen 2 was applied as the layer 2 (red-sensitive emulsion layer), the same emulsion as the layer 4 of the specimen 3 was applies as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 5 was applied as the layer 7 (blue-sensitive emulsion layer).
• Layer 1 Antihalation layer (same as the layer 1 of specimen 1)
• the primitive emulsion 3 was chemically sensitized with gold and sulfur sensitizing agents, it was treated in the same way as the layer 2 of the specimen 1 and then applied.
• Layers 3, 4, 5, 6, 7 and 8 were prepared in the same ways as the layers, 3, 4, 5, 6, 7 and 8 of the specimen 1 respectively, and then applied.
• the specimen 9 was prepared by sequentially applying the layers of the specimen 1 on a cellulose triacetate support in the same way as the specimen 1, except that the layer 4 (green-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 3 with gold and sulfur sensitizing agents and then treating it in the same manner as the layer 4 of the specimen 1.
• the specimen 10 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 2 of the specimen 7 was applied as the layer 2 (red-sensitive emulsion layer), and the same emulsion as the layer 4 of the specimen 9 was applied as the layer 4 (green-sensitive emulsion layer).
• the specimen 11 was prepared by sequentially applying the layers of the specimen 8 on a cellulose triacetate support in the same way as the specimen 8, except that the layer 7 (blue-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 3 with gold and sulfur sensitizing agents and then treating it in the same manner as the specimen 1 in Example 1.
• the specimen 12 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 4 of the specimen 9 was applied as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 11 was applied as the layer 7 (blue-sensitive emulsion layer).
• the specimen 13 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 2 of the specimen 8 was applied as the layer 2 (red-sensitive emulsion layer), the same emulsion as the layer 4 of the specimen 9 was applies as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 11 was applied as the layer 7 (blue-sensitive emulsion layer).
• Layer 1 Antihalation layer (same as the layer 1 of specimen 1)
• Layer 2 Red-sensitive silver halide emulsion layer After the primitive emulsion 4 was chemically sensitized with gold and sulfur sensitizing agents, it was treated in the same way as the layer 2 of the specimen 1 and then applied.
• Layers 3, 4, 5, 6, 7 and 8 were prepared in the same ways as the layers 3, 4, 5, 6, 7 and 8 of the specimen 1 respectively, and then applied.
• the specimen 15 was prepared by sequentially applying the layers of the specimen 1 on a cellulose triacetate support in the same way as the specimen 1, except that the layer 4 (green-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 4 with gold and sulfur sensitizing agents and then treating it in the same manner as the layer 4 of the specimen 1.
• the specimen 16 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 2 of the specimen 14 was applied as the layer 2 (red-sensitive emulsion layer), and the same emulsion as the layer 4 of the specimen 15 was applied as the layer 4 (green-sensitive emulsion layer).
• the specimen 17 was prepared by sequentially applying the layers of the specimen 1 in Example 1 on a cellulose triacetate support in the same way as the specimen 1, except that the layer 7 (blue-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 4 with gold and sulfur sensitizing agents and then treating it in the same manner as the layer 7 of the specimen 1.
• the layer 7 blue-sensitive emulsion layer
• the specimen 18 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 4 of the specimen 15 was applied as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 17 was applied as the layer 7 (blue-sensitive emulsion layer).
• the specimen 19 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 2 of the specimen 14 was applied as the layer 2 (red-sensitive emulsion layer), the same emulsion as the layer 4 of the specimen 15 was applied as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 17 was applied as the layer 7 (blue-sensitive emulsion layer).
• Couplers, colored couplers and preparations of their dispersions used in Examples 1 and 2 were as described below.
• TCP tri-cresyl phosphate
• ethyl acetate 50 g of the aforesaid cyan color forming coupler C-1 and 4 g. of the colored cyan coupler CC-1 were dissolved with heat.
• the solution thus obtained was added to 400 ml. of a 7.5% aqueous gelatin solution containing 4 g. of sodium tri-isopropylnaphthalene sulfonate.
• the mixture was then emulsified and dispersed in a colloid mill and adjusted to 1000 mk.
• the effect of improvement in the image sharpness was evaluated by determining the modulation transfer function (MTF) and comparing the MTF values at a spatial frequency of 30 lines/mm. With respect to blue-sensitive emulsion layer, and 20 lines/mm. with respect to green- and red-sensitive layers.
• MTF modulation transfer function
• specimens 3, 4, 5, 6, 7, 9, 10, 11, 12, 13, 15, 16, 17, 18 and 19 in accordance with the present invention showed the effects of remarkably improving the sharpness in comparison with specimens 1, 2, 8 and 14.
• the regular-crystal emulsion is used in the blue-sensitive emulsion layer which was the uppermost emulsion layer (specimens 5, 6, 7, 11, 12, 13, 17, 18 and 19)
• the sharpness was remarkably improved not only in this blue-sensitive layer but also in the green-sensitive emulsion layer which was positioned below said blue-sensitive emulsion layer.
• the primitive emulsion 5 and 6 were prepared as described below.
• aqueous ammoniacal silver nitrate solution and an aqueous alkali halide solution were precipitated in an aqueous gelatin solution containing alkali halides at 40° C. over 83 minutes by maintaining the pAg value at 9.5 according to the pAg-controlled double jet mixing method.
• a silver iodobromide emulsion having an average crystal size of 0.65 p and a standard deviation of 0.16 ⁇ and containing 5 mol % of essentially cubic silver iodide, with the content of twinned crystals being 8%, was obtained.
• aqueous ammoniacal silver nitrate solution and an aqueous alkali halide solution were admixed with an aqueous gelatin solution containing alkali halides at 40° C. over 20 minutes by maintaining the pAg value at 10.0, and later 40 minutes the pAg value at 10.3 according to the pAg-controlled double jet mixing method.
• a silver iodobromide emulsion having an average crystal size of 0.65 ⁇ and a standard deviation of 0.l49 ⁇ and containing 5 mol % of essentially octahedral silver iodide, with the content of twinned crystals being 8%, was obtained.
• the support was an under-coated cellulose triacetate film. In this way, specimens 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 and 31 were prepared.
• Layer 1 Antihalation layer (same as the layer 1 of specimen 1)
• Layer 2 Red-sensitive silver halide emulsion layer After the primitive emulsion 5 was chemically sensitized with gold and sulfur sensitizing agents, it was treated in the same way as the layer 2 of the specimen 1 and then applied.
• Layers 3, 4, 5, 6, 7 and 8 were prepared in the same ways as the layers 3, 4, 5, 6, 7 and 8 of the specimen 1 respectively, and then applied.
• the specimen 21 was prepared by sequentially applying the layers of the specimen 1 on a cellulose triacetate support in the same way as the specimen 1, except that the layer 4 (green-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 5 with gold and sulfur sensitizing agents and then treating it in the same manner as the layer 4 of the specimen 1.
• the specimen 22 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 2 of the specimen 20 was applied as the layer 2 (red-sensitive emulsion layer), and the same emulsion as the layer 4 of the specimen 21 was applied as the layer 4 (green-sensitive emulsion layer).
• the specimen 23 was prepared by sequentially applying the layers of the specimen 1 in Example 1 on a cellulose triacetate support in the same way as the specimen 1, except that the layer 7 (blue-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 5 with gold and sulfur sensitizing agents and then treating it in the same manner as the layer 7 of the specimen 1.
• the layer 7 blue-sensitive emulsion layer
• the specimen 24 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 4 of the specimen 21 was applied as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 23 was applied as the layer 7 (blue-sensitive emulsion layer).
• the specimen 25 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 2 of the specimen 14 was applied as the layer 2 (red-sensitive emulsion layer), the same emulsion as the layer 4 of the specimen 20 was applies as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 23 was applied as the layer 7 (blue-sensitive emulsion layer).
• Layer 1 Antihalation layer (same as the layer 1 of specimen 1)
• Layer 2 Red-sensitive silver halide emulsion layer After the primitive emulsion 6 was chemically sensitized with gold and sulfur sensitizing agents, it was treated in the same way as the layer 2 of the specimen 1 and then applied.
• Layers 3, 4, 5, 6, 7 and 8 were prepared in the same ways as the layers 3, 4, 5, 6, 7 and 8 of the specimen 1 respectively, and then applied.
• the specimen 27 was prepared by sequentially applying the layers of the specimen 1 on a cellulose triacetate support in the same way as the specimen 1, except that the layer 3 (green-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 6 with gold and sulfur sensitizing agents and then treating it in the same manner as the layer 3 of the specimen 1.
• the specimen 28 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 2 of the specimen 26 was applied as the layer 2 (red-sensitive emulsion layer), and the same emulsion as the layer 4 of the specimen 27 was applied as the layer 4 (green-sensitive emulsion layer).
• the specimen 29 was prepared by sequentially applying the layers of the specimen 1 in Example 1 on a cellulose triacetate support in the same way as the specimen 1, except that the layer 7 (blue-sensitive emulsion layer) was prepared by sensitizing the primitive emulsion 6 with gold and sulfur sensitizing agents and then treating it in the same manner as the layer 7 of the specimen 1.
• the specimen 30 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 4 of the specimen 27 was applied as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 29 was applied as the layer 7 (blue-sensitive emulsion layer).
• the specimen 31 was prepared by sequentially applying the layers on a cellulose triacetate support in the same way as the specimen 1 in Example 1, except that the same emulsion as the layer 2 of the specimen 26 was applied as the layer 2 (red-sensitive emulsion layer), the same emulsion as the layer 4 of the specimen 27 was applied as the layer 4 (green-sensitive emulsion layer), and the same emulsion as the layer 7 of the specimen 29 was applied as the layer 7 (blue-sensitive emulsion layer).

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (4)

Publications (1)

Family

ID=26447008

Family Applications (1)

Country Status (1)

Cited By (4)

Citations (4)

• 1982
  • 1982-07-12 EP EP82303646A patent/EP0070181A1/de not_active Withdrawn

Patent Citations (4)

Similar Documents

Legal Events