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
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
• • 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

• the present invention relates to a silver halide color photographic light-sensitive material, more specifically to a silver halide color photographic light-sensitive material excellent in graininess and color reproduction.
• 923,045 discloses a technique to improve sensitivity without lowering graininess by dividing the emulsion layer into a high-sensitivity layer containing nondiffusible couplers and a low-sensitivity layer which are substantially developed in the same hue, and by controlling the maximum color-developed density in the high-sensitivity emulsion layer at a low level. But this technique is not adequate in providing a good graininess.
• 91945/1987 disclose techniques to improve graininess by forming at least one emulsion layer into a three-layered structure comprised of a low-sensitivity silver halide emulsion layer, medium-sensitivity silver halide emulsion layer and high-sensitivity silver halide emulsion layer, and by controlling finely the maximum color-developed density in each of these layers. But, these techniques cannot necessarily provide satisfactory results.
• IIE spectral sensitivity distribution and inter-image effect
• the object of the present invention is to provide a silver halide color photographic light-sensitive material improved in graininess and color reproduction concurrently.
• the object of the invention can be achieved by a silver halide color photographic light-sensitive material comprising a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, wherein the material satisfies the following requirements:
• Silver halide color light-sensitive materials are frequently used to make enlarged prints.
• a large size such as full size or half size paper sheet
• graininess is satisfactorily improved with the decrease in grain size within the area where the volume average grain size of silver haloide grains is not less than 0.55 ⁇ m, but in the area where the volume average grain size is less than 0.55 ⁇ m, the relation between graininess improvement and grain size is weakened and thereby graininess cannot be improved as expected.
• the surface area of a silver halide emulsion contained in a light-sensitive material can be controlled by changing the coating weight of silver or the shape and size of silver halide grains.
• the coating weight of silver is not more than 7.5 g/m2, preferably not more than 7.0 g/m2 and especially 2.0 to 6.5 g/m2, in view of a good image sharpness, film-forming properties and stability in processing.
• the surface area of silver halide grains can be calculated by the equation of 6 ⁇ d2N, wherein d is volume average grain size and N is number of grains.
• the type of silver halide grains used in the invention is preferably a monodispersed one as described below.
• the term "monodispersion” means that in an emulsion, the weight of silver halide grains contained within the range of volume average grain size d ⁇ 20% is not less than 70% of the total weight of the silver halide grains. In the invention, this value is preferably not less than 80% and especially not less than 90%.
• Specially preferable monodispersed emulsion is ones having a variation coefficient of grain size distribution of 20% or less, most preferable 15% or less. The variation coefficient is defined as follows: The volume average grain size d and standard deviation of grain size distribution are calculated by di which is defined in the later-mentioned.
• substantially monodispersed silver halide grains according to the invention may be used singly, or in combination, at an arbitrary mixing ratio, with two or more types of silver halide grains different in average grain size.
• silver halide grains used in the invention have a core/shell grain structure comprised of two or more layers different in silver iodide content.
• the silver iodide content of the uppermost layer, shell, of said two or more layers is preferably lower than that of the inner layers, core.
• the effect of the invention can be exhibited much obviously by use of silver halide grains containing silver halide grains having a grain structure in which the silver iodide content of the shell is lower than that of the core.
• the silver iodide content of the uppermost layer of silver halide grains be as low as possible, and a content close to 0% is particularly preferred.
• the inner core may be formed so as to have two or more layers different in silver iodide content.
• the difference in silver halide content between a high content layer and a low content layer, which are present between the core and the shell or inside of the core, may form a clear boundary or change continuously without forming a clear boundary.
• the silver iodide distribution in these silver halide grains can be detected by various physical measuring methods. It can be determined, for example, by the measurement of luminescence at a low temperature as described in the Summaries of Lectures at 1981 Convention of Photographic Society of Japan.
• the core/shell type silver halide grains used in the invention consist of a core comprised of silver halide containing silver iodide and a shell which covers the core and is comprised of silver halide having a silver iodide content lower than that of the core, and that the thickness of the shell be 0.001 to 0.2 ⁇ m.
• silver halide grains according to the invention is silver halide grains having a core comprised of silver halide containing 2 to 24 mole% of silver iodide and a shell comprised of silver halide containing 0 to 4 mole% of silver iodide.
• the difference in silver iodide content between the core and the shell is preferably not less than 5 mole%.
• the silver halide component other than the above silver iodide is preferably silver bromide.
• Silver chloride may also be contained as long as it does impair the effect of the invention.
• the average silver iodide content of silver halide grains according to the invention is preferably 0.5 to 15 mole%, especially 5 to 12 mole%.
• the form of silver halide grains of the invention may be any of hexahedron, octahedron, tetradecahedron, tabular, sphere, and a hybrid of these forms. But octahedral or tetradecahedral grains are preferred.
• silver halide grains according to the invention can be prepared by use of monodispersed silver halide grains as cores and covering them with shells.
• Monodispersed core silver halide grains can be prepared in a desired size by the double jet method performed at a constant pAg. Further, the method described in Japanese Pat. O.P.I. Pub. No. 48521/1979 can be applied to the preparation of an emulsion comprised of highly monodispersed silver halide grains.
• such silver halide grains can be prepared by adding an aqueous gelatin solution containing potassium bromide, potassium iodide and an ammoniacal silver nitrate solution to an aqueous gelatin solution containing silver halide grains, while changing the addition speed as a function of time. Proper selection of this addition speed-time function, pH, pAg and temperature provides highly monodispesed silver halide grains.
• the thickness of a shell which covers a core must be thin enough not to conceal the core's desirable properties, and must be thick enough to conceal the core's undesirable properties. Accordingly, the thickness is selected from a range between such an upper limit and lower limits.
• Such a shell can be formed by depositing a silver halide on each of cores consisting of monodispersed silver halide grains, through the addition of a water-soluble halide solution and a water-soluble silver salt solution by the double jet method.
• the volume average size of silver halide grains, contained in the highest sensitivity layer of two or more homochromatic sensitivity sub-emulsion layers constituting the red-sensitive or green-sensitive silver halide emulsion layer is 0.20 ⁇ m to 0.55 ⁇ m, preferably not more than 0.50 ⁇ m, and especially not more than 0.45 ⁇ m.
• volume average size d used here is defined as grain size di at which the product of frequency ni of grains having grain size di and di3 (ni ⁇ di3) takes the largest value (three significant figures, the 4th figure is rounded to the 3rd one).
• size means the length of an edge for cubic grains, and the length of an edge of a cube converted in the same volume for non-cubic grains.
• a blue-sensitive layer contain the following tabular silver halide grains.
• a silver halide emulsion used in the blue-sensitive layer is preferably comprised of tabular silver halide grains, in which at least 50% of the total projected area of all the grains is made up of grains which have an aspect ratio of 3.0 to 7.0 and satisfy the following requisites (a) and (b).
• the aspect ratio means the ratio of grain diameter/grain thickness
• the grain diameter means the diameter of a circle having the same area as the projected area of a grain
• the thickness means the distance between two parallellel planes which constitute a tabular silver halide grain.
• the hexagonal tabular grain preferably usable in the invention possesses a hexagonal (111) face having a side length ratio of 1.0 to 2.0.
• side length ratio means the ratio of the length of the longest side which constitute the hexagon to the length of the shortest side.
• the side length ratio may be 1.0 to 2.0, and the hexagonal may be rounded a little at the corner.
• variable coefficient of grain size means the extent of the grain size variation, and is given in percentage by the value obtained by dividing the standard deviation of diameters of circles converted from projected areas of hexagonal tabular grains (each of which has a side length ratio of 1.0 to 2.0 according to the invention) by the average value of grain sizes.
• variable coefficient of grain thickness means the extent of the thickness variation of hexagonal tabular grains of the invention, and is given in percentage by the value obtained by dividing the standard deviation of thicknesses of hexagonal tabular grains, each of which has a side length ratio of 1.0 to 2.0 according to the invention, by the average value of grain thicknesses.
• At least 50% of the total projected area of the tabular silver halide grains is made up of tabular grains having an aspect ratio of 3.0 to 7.0 as described above. It is preferred that at least 70% of the total projected area be made up of grains having an aspect ratio of 3.0 to 7.0. It is also preferred that at least 50% of the total projected area be made up of grains having an aspect ratio of 3.0 to 4.9.
• At least 70% of the total projected area be made up of grains having an aspect ratio of 3.0 to 4.9.
• At least 70% of the total projected area of the tabular grains is made up of grains having an even number of twin planes parallel to the principal plane, which is a hexagon whose side length ratio is 2.0 to 1.0. It is preferred that at least 90% of the total projected area be made up of such hexagonal tabular grains.
• At least 70% of the total projected area be made up of hexagonal tabular grains having a side length ratio of 1.0 to 1.5. It is particularly preferred that at least 90% of the total projected area be made up of hexagonal tabular grains having a side length ratio of 1.0 to 1.5.
• Chemical sensitization is considerably influenced by the shape, crystal face index, composition and defect of silver halide grains; therefore, mixing-in of grains in such different forms affects the degree of chemical sensitization, and thereby not only hinders chemical sensitization from providing an optimum sensivity and fog, but also allows insufficiently chemical-ripened grains which are easily desensitized by pressure, and excessively chemical-ripened grains which are easily fogged by pressure, to coexist, deteriorating the grains in overall anti-pressure effect characteristics.
• the spectral sensitivity distribution of the blue-sensitive layer of the invention is preferably as follows. That is, the wavelength ⁇ B max which provides the maximum value in the spectral sensitivity distribution of the blue-sensitive layer is within the range of 415 nm ⁇ ⁇ B max ⁇ 470 nm, preferably 420 nm ⁇ ⁇ B max ⁇ 460 nm, and especially within the range of 445 nm + 10 nm.
• the spectral sensitivity at 480 nm is required to be not more than 35%, particularly not more than 25%, of the spectral sensitivity of the blue-sensitive layer at ⁇ B max .
• the tabular silver halide emulsion may use pure silver bromide and silver iodobromide.
• the average silver iodide content in the silver iodobromide is not more than 10 mole%, preferably not more than 8 mole% and especially not more than 6 mole%, in view of color reproducibility.
• use of a silver bromide containing not more than 0.5 mole% of silver iodide is particularly preferred from the viewpoint of color reproducibility, the presence of a little amount of silver iodide exerts a good effect on the stability of the emulsion, and too low a silver iodide content is liable to harden contrast.
• the optimum range of the silver iodide content is 0.1 to 6 mole%, preferably 0.5 to 4 mole% and especially 1 to 3.5 mole%.
• the silver iodide content of each grain can be measured by use of an X-ray microanalyzer.
• the ratio of the standard deviation of silver iodide contents of respective grains measured with an X-ray microanalyzer to the average silver iodide content is defined as a relative standard deviation
• the relative standard deviation is preferably not more than 20%, especially not more than 15%, in view of pressure characteristics of the emulsion.
• the diameter of the hexagonal tabular grain of the invention is not less than 0.4 ⁇ m, preferably 0.5 to 3.0 ⁇ m and especially 0.5 to 1.7 ⁇ m.
• the thickness of the hexagonal tabular grain of the invention is 0.05 to 0.3 ⁇ m, preferably 0.05 to 0.25 ⁇ m and especially 0.05 to 0.20 ⁇ m.
• a sensitizing dye having an absorption spectrum in an objective wavelength region one which provides a silver halide with an objective spectral sensitivity by properly modifying the halide composition and distribution thereof using no sensitizing dye
• a suitable optical light-absorbent in a light-sensitive material incorporating a suitable optical light-absorbent in a light-sensitive material.
• sensitizing dye used in a blue-sensitive silver halide emulsion layer of the light-sensitive material of the invention in order to provide the above spectral sensitivity, but usable sensitizing dyes are not limited to them.
• the DIR compound means a compound which can split off, upon reaction with an oxidation product of a color developing agent, a development inhibitor or a compound capable of releasing a development inhibitor.
• the preferable DIR compounds are those which split off, upon reaction with an oxidation product of a color developing agent, a developing inhibitor or a compound capable of releasing a developing inhibitor, both of which show a diffusibility of not less than 0.34, preferably not less than 0.40, according to the measuring method described below.
• the diffusibility is determined by the following method.
• Sample (I) a sample having a green-sensitive silver halide emulsion layer
• gelatin coating solution containing 0.07 mole per mole silver each of silver iodide spectrally sensitized to green-sensitivity (silver iodide content:6 mole%, average grain size:0.48 ⁇ m) and the following coupler so as to give a silver coating weight of 1.1 g/m2 and a gelatin coating weight of 3.0 g/m2.
• a protective layer is formed thereon by coating a gelation coating solution containing silver iodide subjected to neither chemical sensitization nor spectral sensitization (silver iodide content:2 mole%, average grain size:0.08 ⁇ m) so as to give a silver coating weight of 0.1 g/m2 and a gelatin coating weight of 0.8 g/m2.
• Sample (II) a sample prepared without employing the silver iodide in the protective layer of sample (I)
• Samples (I) and (II) are exposed to white light through an optical wedge, and then processed in the following procedure.
• Composition of the processing solution used in each process is as follows.
• Water is added to make 1 liter, and the pH is adjusted to 6.0 with an aqueous ammonia.
• Water is added to make 1 liter, and the pH is adjusted to 6.0 with acetic acid.
• the DIR compound is preferably one which releases a group having the diffusibility specified above, but any of others may be used.
• Formula (D-1) A-(Y) m where A represents a coupler residue; m represents 1 or 2; and Y represents a group bonding with coupler residue A at the coupling position, which splits off upon reaction with an oxidation product of a color developing agent to release a development inhibitor or a developing inhibitor precursor.
• Y is typically represented by following Formulas (D-2) to (D-19).
• Rd1 represents a hydrogen or halogen atom, or an alkyl, alkoxy, acylamino, alkoxy, carbonyl, thiazolidinydene amino, aryloxycarbonyl, acyloxycarbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino group.
• n 0, 1 or 2; when n is 2, two Rd1s may be the same or different.
• the total number of carbon atoms contained in n Rd1s is 0 to 10.
• the number of carbon atoms contained in Rd1 in Formula (D-6) is 0 to 15.
• X in Formula (D-6) represents an oxygen or sulfur atom.
• Rd2 represents an alkyl, aryl or heterocyclic group.
• Rd3 represents a hydrogen atom, or an alkyl, cycloalkyl, aryl or heterocyclic group.
• Rd4 represents a hydrogen or halogen atom, or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamido, cyano, heterocyclic, alkylthio or amino group.
• the alkyl group represented by Rd1, Rd2, Rd3 or Rd4 may have a substituent, and may be either straight-chain or branched.
• the aryl group represented by Rd1, Rd2, Rd3 or Rd4 may have a substituent.
• the heterocyclic group represented by Rd1, Rd2, Rd3 or Rd4 may have a substituent.
• the heterocyclic group is preferably a 5- or 6-membered monocycle or condensed ring containing a heteroatom selected from nitrogen, oxygen and sulfur; examples thereof include pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, tiazolyl, triazolyl, benzotriazolyl, imido and oxazinyl groups.
• the number of carbon atoms contained in Rd2 of Formulas (D-6) and (D-8) is 0 to 15.
• the TIME group is a group which bonds with A at its coupling position and can split off upon reaction with an oxidation product of a color developing agent. After splitting off from the coupler, this can release an INHIBIT group at a properly controlled rate.
• the INHIBIT group is a group which acts, when released, as a development inhibitor represented, for example, by Formulas (D-2) to (D-9).
• the TIME-INHIBIT group in Formula (D-10) is typically represented by following Formulas (D-11) to (D-19)
• Rd5 represents a hydrogen or halogen atom, or an alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, hydroxy or alkanesulfonyl group.
• 1Rd5s may link to each other to form a condensed ring.
• each Rd5 represents an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
• Rd7 represents a hydrogen atom, or an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
• Rd8 and Rd9 each represent a hydrogen atom or an alkyl group (preferably, one having 1 to 4 carbon atoms).
• k represents an integer of 0, 1 or 2.
• 1 represents an integer of 1 to 4.
• m represents an integer of 1 or 2; when n is 2, two Rd7s may be the same or different.
• n represents an integer of 2 to 4, and n Rd8s and n Rd9s may be the same or different.
• B represents an oxygen atom or (Rd6 is the same as that defined above).
• the number of carbon atoms contained in each Rd1 of Formulas (D-2) to (D-7) is 0 to 32 in total
• the number of carbon atoms contained in Rd2 of Formula (D-8) is 1 to 32
• the number of carbon atoms contained in Rd3 and Rd4 is 0 to 32 in total.
• DIR compounds preferred ones are those whose Y is represented by Formula (D-2), (D-3) or (D-10); among ones represented by Formula (D-10), the preferred are those whose INHIBIT group is represented by Formula (D-2), (D-6), particularly preferred one is that whose X in Formula (D-6) is an oxygen atom, or (D-8), particularly preferred one is that whose Rd2 in Formula (D-8) is a hydroxyaryl or alkyl group having 1 to 3 carbon atoms.
• Examples of the coupler component represented by A in Formula (D-1) include yellow dye image forming coupler residues, magenta dye image forming coupler residues, cyan dye image forming coupler residues and non-color forming coupler residues.
• DIR compounds described in U.S. Pat. Nos. 4,234,678, 3,227,554, 3,617,291, 3,958,993, 4,149, 886, 3,933,500, 2,072,363, 2,070,266, Japanese Pat. O.P.I. Pub. No. 56837/1982 and Research Disclosure No. 21,228 (December, 1981).
• At least one, more preferably at least two of the light-sensitive layers contains a DIR compound. It is preferable that a light-sensitive layer contains two or more kinds of DIR compounds different from each other in the diffusibility of development inhibitor or its precursor spritted off therefrom. In the invention, it is preferred to combine a DIR compound having an aforesaid diffusibility of 0.34 to less than 0.4 with a DIR compound having an aforesaid diffusibility of not less than 0.4.
• the molar quantity of the DIR compound capable of releasing a high diffusible inhibitor is not less than 3 times, preferably not less than 5 times, and especially not less than 7 times that of the DIR compound capable of releasing a low diffusible inhibitor contained in the same layer.
• Preferable examples of the DIR compound having an aforesaid diffusibility of less than 0.4 are those exemplified above bearing the number of D-21, D-23, D-29, D-31, D-33, D-34 or D-37.
• DIR compound having an aforesaid diffusibility of not less than 0.4 are those exemplified above with the number of D-6, D-7, D-17, D-24, D-25, D-26, D-27 or D-32.
• the preferable addition amount of the DIR compound is 1.0 ⁇ 10 ⁇ 4 to 1.0 ⁇ 10 ⁇ 1 mole, more preferably 4.0 ⁇ 10 ⁇ 4 to 5.0 ⁇ 10 ⁇ 2 mole, and especially 8.0 ⁇ 10 ⁇ 4 to 2.0 ⁇ 10 ⁇ 2 mole per mole of silver halide.
• DIR compounds described, for example, in U.S. Pat. Nos. 4.234,676, 3,227,554, 3,617,291, 3,958,993, 4,149,886, 3,933,500, 2,072,363, 2,070,266, Japanese Pat. O.P.I. Pub. Nos. 56837/1982, 13239/1976 and Research Disclosure No. 21228 (December, 1981).
• the using amount of the diffusible DIR compound in the invention is required to meet the relation to the surface area of silver halide grains as described above. And it is preferably not less than 2.0 ⁇ 10 ⁇ 4 mole/m2, more preferably 5.0 ⁇ 10 ⁇ 4 to 2 ⁇ 10 ⁇ 3 mole/m2 all over a light-sensitive material, when shown as an amount per mole of silver halide.
• the diffusible DIR compound may be used in an arbitrary manner, but it is preferred to be used at least in the highest sensitivity layers of red-sensitive layers and green-sensitive layers, respectively.
• the diffusible DIR compound be distributed in layers so as to give an IIE which satisfy the following requirements; that is, maximum gradations obtained by monochromatic exposure with respective wavelengths in the vicinity of spectral sensitivity peaks of red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers, ⁇ R P , ⁇ G P and ⁇ B P , are 0.80 ⁇ ⁇ R P 0.70 ⁇ ⁇ R P 0.70 ⁇ ⁇ G P 0.70 ⁇ ⁇ B P and gradations obtained by standard white light exposure, ⁇ R , ⁇ G and ⁇ B , are 0.65 ⁇ ⁇ R 0.65 ⁇ ⁇ G 0.75 ⁇ ⁇ B
• the layer configuration of low speed sub-emulsion layer-high speed sub-emulsion layer is used; when the emulsion layer is comprised of three sub-emulsion layers different
• the layer configuration is not necessarily bound to the above ones of the high speed layer, but the effect of the invention can be much exhibited with a configuration where a high speed sub-emulsion layer is provided farthest from a support.
• the sensitivity difference between homochromatic sub-emulsion layers be from 0.1 to 1.0 in ⁇ log E.
• couplers can be employed in the invention, typical examples thereof are seen in the above numbers of Research Disclosure.
• Additives usable in the invention can be added according to such a dispersion method as is described in RD308119 XIV.
• supports described in RD17643, p.28, RD18716, pp.647-8 or RD308119, XVII can be used.
• the light-sensitive material of the invention may have auxiliary layers such as filter layer and intermediate layer described in RD308119, VII, sec. K.
• the invention can be applied to a variety light-sensitive materials represented by negative film for general purposes or for movies, color reversal film for slides or TV, color paper, color positive film and color reversal paper.
• the light-sensitive material of the invention can be processed in conventional procedures described in RD 17643, pp.28-29, RD18716, p.647 and RD308119, XVII.
• the addition amount to a silver halide photographic light-sensitive material is given in grams per 1 m2, unless otherwise specified.
• the amounts of silver halide and colloidal silver are given as an amount of silver present.
• Multilayer color photographic light-sensitive material sample 101 was prepared by forming, on an acetyl cellulose film support, layers respectively having the following compositions in numerical order from the support side.
• 1st layer antihalation layer (HC) Black colloidal silver 0.15 g UV absorbent (UV-1) 0.20 g Compound (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling solvent (Oil-2) 0.20 g Gelatin 1.6 g 2nd layer: intermediate layer (IL-1) Gelatin 1.3 g 3rd layer: low speed red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (volume average grain size: 0.3 ⁇ m) 0.50 g Silver iodobromide emulsion (volume average grain size: 0.46 ⁇ m) 0.50 g Sensitizing dye (S-1) 3.2 ⁇ 10 ⁇ 4 mole/mole Ag Sensitizing dye (S-2) 3.2 ⁇ 10 ⁇ 4 mole/mole Ag Sensitizing dye (S-3) 0.2 ⁇ 10 ⁇ 4 mole/mole Ag Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) 0.13 g
• the silver iodobromide emulsion used in the 10th layer was prepared in the following procedure.
• a silver iodobromide emulsion was prepared by the double jet method by use of seed grains comprised of monodispersed silver iodobromide grains having an average grain size of 0.33 ⁇ m and a silver iodide content of 2 mole%.
• the pAg and pH were controlled by use of an aqueous solution of potassium bromide and 56% acetic acid.
• the grains formed were subjected to desalting according to a usual flocculation method, and then dispersed again with the addition of gelatin. Then, the pH and pAg were adjusted to 5.8 and 8.06, respectively, at 40°C.
• the emulsion prepared as above was a monodispersed emulsion comprised of octahedral silver iodobromide grains having a volume average grain size of 0.8 ⁇ m, a grain size distribution extent of 12.4% and a silver iodide content of 8.5 mole%.
• the other emulsions different in volume average grain size and silver iodide content were prepared in similar manners as the above, by varying the average size of seed grains, temperature, pAg, pH, flow rate, addition time and halide composition.
• Each of these emulsions was a monodispersed emulsion comprised of core/shell type grains having a grain size distribution extent of not more than 20%.
• Each emulsion was subjected to an optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid ammonium thiocyanate; then, sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added thereto.
• the above light-sensitive material 101 further contained compounds SU-1, SU-2, viscosity conditioner, hardeners H-1, H-2, stabilizer ST-1, antifoggants AF-1, AF-2 (respective weight average molecular weights were 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1 (9.4 mg/m2).
• light-sensitive material 102 was prepared by changing the components as follows. The layers omitted had the same content as that in 101.
• 3rd layer R-L Silver iodobromide emulsion (volume average grain size: 0.27 ⁇ m) 1.0 g Sensitizing dye (S-1) 4.5 ⁇ 10 ⁇ 4 mole/mole Ag Sensitizing dye (S-2) 4.5 ⁇ 10 ⁇ 4 mole/mole Ag Sensitizing dye (S-3) 0.28 ⁇ 10 ⁇ 4 mole/mole Ag Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.0010 mole/mole Ag DIR compound (D-3) 0.0024 mole/mole Ag High boiling solvent (Oil-1) 0.55 g Gelatin 1.0 g 4th layer: R-H Silver iodobromide emulsion (volume average grain size: 0.27 ⁇ m)
• Light-sensitive materials 103 to 109 each having the composition shown in Table 1 were prepared in similar manners as above. In preparing them, the amounts of DIR compound (D-1) and couplers were varied a little with layers in order to make their gradations close to one another as much as possible.
• Light-sensitive materials 101 to 109 prepared as above were evaluated for the following properties.
• Light-sensitive materials 101 to 109 were subjected to white light exposure through an optical step wedge for sensitometry and then processed under the conditions described later.
• the RMS value of each processed sample was measured at a color developed portion having a density of Dmin (minimum density) + 0.4.
• the RMS value was determined by scanning the density of a measured portion of a sample with a microdensitometer with an scanning aperture of 1800 ⁇ m2 (slit width: 10 ⁇ m, slit length: 180 ⁇ m) and multiplying the standard deviation of variation in densities (of more than 1000 samplings) by 1000.
• a color rendition chart made by Macbeth Co. (a color chart consisting of 18 colored patterns and 6 achromatic patterns) was photographed with light-sensitive materials 101 to 109, followed by the processing described above.
• the photographed patterns were printed on color paper (PC paper Type SR made by Konica Corp.) from the processed film, so as to print the gray of optical density 0.7 in the same density.
• PC paper Type SR made by Konica Corp.
• the processing was made as follows. Processing Processing time Processing temprature Replenishing amount* Color developing 3 min 15 sec 38 ⁇ 0.3°C 780 ml Bleaching 45 sec 38 ⁇ 2.0°C 150 ml Fixing 1 min 30 sec 38 ⁇ 2.0°C 830 ml Stabilizing 60 sec 38 ⁇ 5.0°C 830 ml Drying 1 min 55 ⁇ 5.0°C * The amount is per m2 of light-sensitive material.
• compositions of the color developer, bleaching solution, fixer, stabilizer and their replenishers are as follows.
• Color developer Water 800 ml Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)-aniline sulfate 4.5 g Diethylenetriaminepentacetic acid 3.0 g Potassium hydroxide 1.2 g
• the pH is adjusted to 4.0 with an aqueous ammonia or glacial acetic acid, and then water is added to make 1 liter.
• the pH is adjusted to 6.2 with an aqueous ammonia or glacial acetic acid, and then water is added to make 1 liter.
• the pH is adjusted to 6.5 with an aqueous ammonia or glacial acetic acid, and then water is added to make 1 liter.
• Stabilizer and its replenisher Water 900 ml Octyl-phenyl polyethylene oxyether (average polymerization degree: 10) 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazoline-3-one 0.1 g Siloxane (L-77 made by UCC) 0.1 g Aqueous ammonia 0.5 ml
• Water is added to make 1 liter, and the pH is adjusted to 8.5 with an aqueous ammonia or 50% sulfuric acid.
• the graininess and color reproduction cannot be improved concurrently by changing the size of silver halide grains or by a merely increase in addition amount of diffusible DIR compounds; the improvement can be made only when a specific relation is valid between the sum of the surfaces of light-sensitive silver halide grains and the amount of diffusible DIR compounds used.
• Light-sensitive material 110 was prepared by changing the silver halide emulsions, sensitizing dyes and DIR compounds used in the 9th and 10th layers of light-sensitive material 109 in Example 1 as shown below. In addition to the evaluation in Example 1, a bluish green cloth was photographed, and prints were made from the processed film as in Example 1. Comparison of the image of the cloth on the print with the original bluish green cloth showed that the reproduced color was much closer to the original color, as compared with the result obtained by sample 109.
• color reproduction of the bluish green can also be improved by incorporating tabular silver halide grains in the bule-sensitive layer and controlling the spectral sensitivity distribution of the blue-sensitive layer in accordance with the invention.
• B-L Tabular silver iodobromide grain emulsion (volume average grain size: 0.30 ⁇ m, aspect ratio: 4.00) 0.60 g Sensitizing dye (A-7) 7.3 ⁇ 10 ⁇ 4 mole/mole Ag Yellow coupler (Y-1) 0.60 g Yellow coupler (Y-2) 0.32 g DIR compound (D-2) 0.0030 mole/mole Ag High boiling solvent (Oil-2) 0.18 g Gelatin 1.30 g 10th layer: B-H Tabular silver iodobromide grain emulsion (volume average grain size: 0.42 ⁇ m, aspect ratio: 4.40) 0.50 g Cubic silver iodobromide grain emulsion (volume average grain size: 0.65 ⁇ m) 0.20 g Sensitizing dye (A-7) 8.3 ⁇ 10 ⁇ 4 mole/mole Ag Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g DIR compound (D-1) 0.00003 mo

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• 1991
  • 1991-03-04 JP JP3761491A patent/JPH04275544A/ja active Pending
• 1992
  • 1992-03-04 EP EP19920103658 patent/EP0507092A3/en not_active Withdrawn

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