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
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
• • 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
  • G03C2007/3027—Thickness of a layer

Definitions

• the present invention relates to a silver halide color photographic light-sensitive material, and, particularly, to a silver halide color photographic light-­sensitive material that can achieve an improved image quality and an improved storage stability.
• the silver halide color photographic materials are formed with plural color-sensitive layers, and on the other hand an effort is made for reducing the thickness of photographic component layers of the light-sensitive materials according to the demand for achieving the high image quality.
• an oxidized product of a developing agent may react in a higher speed layer adjacent to a lower speed layer with a coupler present in said higher speed layer and thereafter an excessive oxidized product may diffuse even in the lower speed layer to react with a coupler present in said lower speed layer, causing a lowering of the graininess in the lower speed layer because of the so-called diffusion projection effect, and bringing about a situation in which the image irregularity is caused.
• An object of the present invention is to provide a silver halide color photographic light-sensitive material that can have a good graininess and sharpness of an image and have an excellent image quality and development processing stability.
• a silver halide color photographic light-sensitive material comprising a support having thereon at least two silver halide emulsion layers having the same color sensitivity and different speed from each other and at least one non-light-sensitive hydrophilic colloid layer, wherein said hydrophilic colloid layer is interposed between a higher speed layer and a lower speed layer of said silver halide emulsion layers, and said higher speed layer has a dry layer thickness of 1.6 ⁇ or less and said hydrophilic colloid layer has a dry layer thickness of 0.2 to 1.5 ⁇ .
• the non-light-sensitive hydrophilic colloid layer is interposed between a higher speed layer and a lower speed layer of the silver halide emulsion layers.
• hydrophilic colloid layer there is used gelatin, protein, or synthetic hydrophilic polymers, and particularly may preferably be used gelatin.
• the hydrophilic colloid layer is non-light-sensitive, and being non-light-sensitive is meant to be not sensitive to the exposure when an image is exposed to light or sensitive to light in a negligible degree.
• the presence of such an intermediate layer can effectively prevent the diffusion projection effect originating from the higher speed layer.
• said layer in order to more enhance the effect of preventing the same, it is possible for said layer to contain a substance capable of reacting an oxidized product diffusing from the higher speed layer into said layer.
• the intermediate layer may be interposed between the higher speed layer and the lower speed layer, but may preferably be in direct contact with the higher speed layer and the lower speed layer.
• the above silver halide emulsion layers are comprised of at least two layers having the same color sensitivity and different speed from each other.
• the "same color sensitivity" herein used refers to a property of absorbing the light of the wavelength of substantially the same wavelength region.
• Such color sensitive layers may be of a single color or multi-colors, but preferably of multi-­colors. Particularly preferred is a full color type, and in the case of the full color type they are formed with the provision of a blue-sensitive emulsion layer, a green-­sensitive emulsion layer and a red-sensitive emulsion layer.
• the above color sensitive layers generally include a blue-sensitive layer, a green-sensitive layer and a red-­sensitive layer, and when used for the full color type, all of these color sensitive layers are laminated to from the layers.
• the present invention can be particularly effective in the green-sensitive layer.
• the above green-sensitive layer contains a magenta coupler, and as the magenta coupler, there can be preferably used known 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazolotriazole type couplers and open chain acylacetonitrile type couplers.
• the red-sensitive layer contains a cyan coupler, and as the cyan coupler, there can be preferably used naphthol type couplers and phenol type couplers.
• the blue-sensitive layer contains a yellow coupler, and as the yellow coupler, there can be preferably used, for example, acylacetanilide type couplers. Among these, preferred are benzoylacetanilide type and pivaloylacetanilide type compounds.
• the highly color-forming coupler various types have been reported, including, for example, the polymer couplers described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) 36249/1984, the pyrazolotriazole type magenta couplers and benzoyl type yellow couplers described Japanese Patent O.P.I. Publication No.246748/1986. Accordingly, it is preferable to use the highly color-forming couplers as a means for reducing the thickness.
• the silver halide emulsion layers are further provided with the higher speed layer and the lower speed layer.
• the terms "higher speed” and “lower speed” herein used are based on a strictly relative evaluation.
• the intermediate speed layer corresponds to the lower speed layer mentioned in the present invention when, for example, the hydrophilic colloid layer is interposed between the respective high speed layer and intermediate speed layer, or the intermediate speed layer corresponds to the higher speed layer mentioned in the present invention when it is interposed between the intermediate speed layer and the low speed layer.
• the emulsion layers preferably used may preferably have a difference in the sensitivity between the respectively adjacent layers, generally of 0.1 to 1.0 in log E (E represents an exposure amount).
• E represents an exposure amount.
• the gradation of an image can be controlled by providing at least two of such layers having the same color sensitivity and different speed from each other.
• control of sensitivity is carried out generally by changing the grain size of silver halide grains contained in the silver halide emulsion layers, and the control of sensitivity in the present invention can be carried out by use of the means like this or any other various means.
• the higher sensitivity layer have a dry layer thickness of 1.6 ⁇ or less, preferably 0.5 to 1.5 ⁇ .
• the layer thickness of more than 1.6 ⁇ may cause a strong tendency of the scattering of transmitted light in said higher speed layer, resulting in the deterioration of sharpness.
• an overly thin layer thickness may result in no practical usefulness in relation to silver halide emulsions, additives, etc., giving a lower limit to be necessarily set up.
• the dry layer thickness refers to a layer thickness measured under the conditions in which the humidity has been controlled to 55 % at 23°C.
• the layer thickness in the plurality of layers can be determined by taking an enlarged photograph with use of a scanning electron microscope and measuring the layer thickness of the respective layers.
• the lower limit of the total of the dry layer thickness of all the hudrophilic colloid layers in the above photographic component layers has the limit as mentioned above depending on the volume held by silver halide emulsion layers, oily agents such as couplers, additives, and binders such as gelatin, and the layer thickness on the emulsion layer side may preferably be in the range of 5 ⁇ to 8 ⁇ , more preferably 10 ⁇ to 16 ⁇ .
• the thickness from an outermost surface of the emulsion layer side to the bottom end of an emulsion layer nearest to the support may preferably be 14 ⁇ or less, and the thickness therefrom to the bottom end of an emulsion layer having the color sensitivity different from the first-mentioned emulsion layer and near to the support in the next place of the first-mentioned emulsion layer may preferably be 10 ⁇ or less.
• a silver halide emulsion forming the above color-­sensitive layer will be described below.
• the silver halide emulsion there can be used any of those used as silver halides in usual silver halide emulsion layers, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride, but preferred is an emulsion in which silver iodobromide is used.
• Silver halide grains used in the silver halide emulsion may be any of those obtained by an acidic method, a neutral method and an ammoniacal method. The grains may be allowed to grow at one time, or grow after seed grains have been formed.
• the manner to prepare the seed grains and the manner to grow them may be same or different.
• the silver halide emulsion containing such grains may be obtained by simultaneously mixing halide ions and silver ions, or by preparing an aqueous solution in which either one of them is present and then mixing in it the other of them.
• it may be formed by successively simultaneously adding halide ions and silver ions while controlling pH and pAg in a mixing vessel. According to this method, it is possible to obtain silver halide grains that are regular in crystal form and substantially uniform in grain size. it is also possible to change the silver halide formulation in the grains after growth, with use of a conversion method.
• the silver halide emulsion there may be used those having any grain size distribution.
• a emulsion having a broad grain size distribution (called a polydispersed emulsion), or may be used an emulsion having a narrow grain size distribution (called a monodispersed emulsion), which may be used alone or as a mix of several kinds.
• a mixture of the polydispersed emulsion and monodispersed emulsion may also be used.
• the monodispersed emulsion is the monodispersed emulsion.
• the "monodispersed" in the monodispersed emulsion is meant to be an emulsion having the variation coefficient in the grain size distribution of the silver halide grains to be contained in the silver halide emulsion, of 22 % or less, preferably 15 % or less.
• the variation coefficient refers to a coefficient showing the width of grain size distribution, and can be defined by the formulas shown below.
• ri represents grain size of the respective grains
• ni the number thereof.
• the average grain size indicates the length of a side in the case of a cubic silver halide grain, and, in the case of a spherical one, an average value of the length of a side when converted into a cube.
• the above grain size can be measured according to all sort of methods generally used for the above purpose in the present technical field.
• a typical method is described in "Method for Analysis of Grain Size", A.S.T.S. Symposium on Light Microscopy, 1955, pp.94-122, or Chapter II in "The Theory of The Photographic Process", coauthored by Meas and James, Third Edition, published by Macmillan Publishing Co., Inc. (1966).
• the present invention can be effective for improving the graininess if the "compound that captures an oxidized product of a color developing agent but does not contribute to the image formation" described in Japanese Patent O.P.I. Publication No. 205343/­1987 is contained in at least the higher speed layer.
• Particularly effective as the above compound is a gallic acid derivative. It may be added preferably in an amount of 4.0 x 10 ⁇ 5 mol to 3.5 x 10 ⁇ 2 mol, more preferably 4.0 x 10 ⁇ 4 mol to 1.7 x 10 ⁇ 2 mol, per mol of silver halide contained in an emulsion layer.
• To add the compound in an emulsion it may be added by dissolving a given amount of the above compound in an organic solvent such as methanol, or may be added by dispersing it together with couplers or singularly.
• the above hydrophilic colloid layer may have a dry layer thickness of 0.2 to 1.5 ⁇ , more preferably 0.3 to 1.0 ⁇ .
• a dry layer thickness of 0.2 to 1.5 ⁇ In the absence of this layer, there can be obtained no action of preventing the diffusion projection effect owing to the higher speed layer, causing a lowering of the graininess of the lower speed layer.
• the layer thickness less than 0.2 ⁇ may result similarly.
• the layer thickness more than 1.5 ⁇ may cause a lowering of the permeability of the developing agent to deteriorate the developing performance, and also cause a lowering of the transmittance of light to deteriorate the graininess.
• a diffusible DIR compound can be preferably used.
• the diffusible DIR compound refers to a compound whose diffusibility of a development inhibitor or of a compound capable of releasing a developing inhibitor, which is capable of being split off from the DIR compound through the reaction with an oxidized product of a color developing agent, is 0.40 or more in terms of the diffusibility according to the evaluation method described below.
• the diffusibility can be evaluated according to the following method:
• Sample (I) A sample having a green-sensitive silver halide emulsion layer.
• a gelatinous coating solution containing silver iodobromide having been spectrally sensitized to have green sensitivity (silver iodide: 6 mol %; average grain size: 0.48 ⁇ m) and 0.07 mol, per mol of silver, of the coupler shown below is coated to have a coated silver amount of 1.1 g/m2 and a gelatin amount of 3.0 g/m2, and a gelatinous coating solution containing silver iodobromide having been not chemically sensitized nor spectrally sensitized (silver iodide: 2 mol %; average grain size: 0.08 ⁇ m) is coated thereon as a protective layer to have a coated silver amount of 0.1 g/m2 and a gelatin amount of 0.8 g/m2.
• Sample (II) A sample in which the silver iodobromide has been removed from the protective layer.
• a hardening agent and a surface active agent are contained in addition to the above.
• Samples (I) and (II) are exposed to white light with use of a wedge, followed by processing according to the processing method shown below.
• Processing solutions used in the respective processing steps have the formulation as follows.
• Ferric ammonium ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Made up to 1 liter by adding water, and adjusted to pH 6.0 with use of ammonia water.
• Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Made up to 1 liter by adding water, and adjusted to pH 6.0 with use of acetic acid.
• Formalin (a 37 % aqueous solution) 1.5 ml Konidax (produced by Konishiroku Photo Industry Co., Ltd.) 7.5 ml Made up to 1 liter by adding water.
• Desensitization degree of sample (I): ⁇ S S0 - S I
• any types of the compound can be used without regard to their chemical structure so long as the diffusibility of the released group is in the above range.
• A represents a coupler residual group
• m represents 1 or 2
• Y represents a group capable of bonding to the coupling position of the coupler residual group A and capable of being split off through the reaction with an oxidized product of a color developing agent, and is a development inhibiting group or a group capable of releasing a development inhibitor, having 0.40 or more of diffusibility.
• Y is typically represented by any of General Formulas (D-2) to (D-19) shown below.
• Rd1 represents a hydrogen atom, a halogen atom, or an alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolylideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-­dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino group; and n represents 0, 1 or 2, and Rd1 may be the same or different when n is 2.
• the sum of the number of the carbon atoms contained in n of Rd15 is 0 to 10. Also,
• X represents an oxygen atom or a sulfur atom.
• Rd2 represents an alkyl group, aryl group or heterocyclic group.
• Rd3 represents a hydrogen atom, or an alkyl, cycloalkyl, aryl or heterocyclic group
• Rd4 represents a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamide, cyano, heterocyclic, alkylthio or amino group.
• Rd1, Rd2, Rd3 or Rd4 represents an alkyl group
• this alkyl group may include those having a substituent and may be any of straight chain or branched alkyls.
• Rd1, Rd2, Rd3 or Rd4 represents an aryl group
• the aryl group may include those having a substituent.
• this heterocyclic group may include those having a substituent, and preferably include a single ring or condensed ring of 5 or 6 members containing as a hetero atom at least one selected from a nitrogen atom, an oxygen atom and a sulfur atom, for example, a pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide or oxazine group.
• -TIME- represents a group capable of entering into combination with the coupling position of A and undergoing cleavage through the reaction with an oxidized product of a color developing agent, and is a group capable of releasing an -INHIBIT group with appropriate control, after cleavage from a coupler.
• the -INHIBIT group is a group formed into a development inhibiter by the above releasing (e.g. the group represented by any of the above Formulas (D-2) to (D-9)).
• the -TIME-INHIBIT- group is typically represented by any of Formulas (D-11) to (D-19) shown below.
• Rd5 represents a hydrogen atom, or an alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, hydroxyl or alkanesulfonyl group.
• Rd5 may each other combine to form a condensed ring.
• Rd6 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 in Formula (D-19) each represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms); k in Formulas (D-11) and (D-­15) to (D-18) represents an integer of 1 or 2; in Formulas (D-11) to (D-13), (D-15) and (D-18) represents an integer of 1 to 4; m in Formula (D-16) represents an integer of 1 or 2, and the respective Rd7 may be the same or different when m is 2; n in Formula (D-19) represents an integer of 2 to 4, and Rd8 and Rd9 in the number of n may each be the same or different; B in Formulas (D-16) to (D-18) represents an oxygen atom or (Rd6 has the same meaning as defined above); in Formula (D-16) indicates that the bond may be either a single bond or a double bond, wherein m is 2 when it is a single bond, and m is 1 when it is a double bond; and INHI
• the sum of the number of carbon atoms contained in Rd1 in Formulas (D-2) to (D-7) is 0 to 32, that of the number of the carbon atoms contained in Rd2 in Formula (D-8) is 1 to 32, and that of the number of the carbon atoms contained in Rd3 and Rd4 in Formula (D-9) is 0 to 32.
• Rd5, Rd6 and Rd7 each represent an alkyl group, an aryl group or a cycloalkyl group, they may include those having a substituent.
• Y is represented by Formula (D-2), (D-3) or (D-10).
• D-10 preferred are those wherein INHIBIT is represented by Formulas (D-2), (D-6) (particularly when X in Formula (D-6) is an oxygen atom) or (D-8) (particularly when Rd2 in Formula (D-8) is a hydroxyl aryl group or an alkyl group having 1 to 3 carbon atoms).
• the coupler component represented by A in Formula (D-­1) may include a yellow dye image-forming coupler residual group, a magenta dye image-forming coupler residual group, a cyan dye image-forming coupler residual group, and non-­coloring coupler residual group.
• Examples of the diffusible DIR compound used in working the present invention include the compounds as shown below, but by no means limited to these.
• the groups are specified by the number in the parentheses.
• the groups corresponding to the respective numbers are listed at the end of this exemplary compound, hereinafter having the same meaning in specifying the exemplary compounds.
• additives can be added in the photographic component layers formed by the above emulsions and so forth, and all kinds of photographic additives such as a wetting agent, a film property improver and a coating auxiliary can be also added depending on the purpose.
• photographic additives there can be further used a plasticizer, a surface active agent, an ultraviolet absorbent, a pH adjuster, an antioxidant, an antistatic agent, a thickening agent, a graininess improver, a dye, a mordant, a brightening agent, a development speed regulator, a matting agent, and so forth.
• the ultraviolet absorbent for example, thiazolidone, benzotriazole, acrylonitrile or benzophenone compounds.
• a suitable gelatin derivative can be used as a protective colloid or binding agent (binder) depending on the purpose, in additon to gelatin, and other hydrophilic binding agent (binder) can be also contained depending on the purpose.
• binding agent a protective colloid or binding agent
• other hydrophilic binding agent binder
• They can be added in the photographic component layers such as an emulsion layer, an intermediate layer, a protective layer, a filter layer and a subbing layer in the above light-­sensitive photographic material, and the above hydrophilic binder may further contain a suitable plasticizer or wetting agent depending on the purpose.
• the photographic component layers of the above light-­sensitive material can also be hardened with use of a suitable hardening agent.
• the silver halide color photographic light-sensitive material according to the present invention is particularly suited for a negative light-sensitive photographic material.
• the amount for the addition in the silver halide photographic light-sensitive material indicates an amount per 1 m2, unless particularly mentioned.
• Silver halide and colloidal silver are indicated in terms of silver.
• gelatin-hardening agents (H-1) and (H-2) and a surface active agent were added in addition to the above composition.
• Ferric ammonium ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Made up to 1 liter by adding water, and adjusted to pH 6.0 with use of ammonia water.
• Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Made up to 1 liter by adding water, and adjusted to pH 6.0 with use of acetic acid.
• Formalin (a 37 % aqueous solution) 1.5 ml Konidax (produced by Konishiroku Photo Industry Co., Ltd.) 7.5 ml Made up to 1 liter by adding water.
• the RMS value was indicated in terms of a 1,000 time value of the standard deviation of the variation in density values caused when the density at minimum density + 1.0 was scanned with a microdensitometer having an open scanning area of 250 ⁇ m2.
• the samples other than those marked with "*" are those in which 8.5 x 10 ⁇ 4 mol of gallic acid ester per mol of silver was added by dispersing it simultaneously with the couplers.
• the storage stability was evaluated by the sensitivity (S) and gamma value ( ⁇ ) of the images obtained by the above respective samples, after unexposed light-­sensitive materials were stored for 3 days in an environment of a temperature of 50°C and a relative humidity of 80 %.
• the developing performance was evaluated by the sensitivity (S) and gamma value ( ⁇ ) of the above respective samples, obtained when processed with use of respective developing solutions, using color developing solutions whose pH was set to 9.90 and 10.20.

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Citations (5)

• 1986
  • 1986-12-03 JP JP28673386A patent/JPS63141044A/ja active Pending
• 1987
  • 1987-12-02 EP EP87310596A patent/EP0270351A3/en not_active Withdrawn

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