Silver halide color photographic material

FIELD OF THE INVENTION
The present invention relates to a silver halide color photographic material, more specifically, to a silver halide color photographic material excellent in color reproducibility and also in processing stability.
BACKGROUND OF THE INVENTION
The color reversal photographic material is demanded to provide excellent image quality the same as in a color negative photographic material.
As a means for improving the image quality, known is the method of adding a light-insensitive silver halide grain or colloidal silver to a light-sensitive emulsion layer and/or to a layer adjacent to the light-sensitive layer. For example, JP-A-51-128528 (corresponding to U.S. Pat. No. 4,082,553, the term "JP-A" as used herein means an "unexamined published Japanese patent application") describes a color reversal photographic material comprising a silver halide emulsion layer containing a silver halide grain with the surface being fogged to improve the interlayer effect. Further, JP-A-60-126652, JP-A-63-304252, JP-A-2-110539, JP-A-3-113438 and U.S. Pat. No. T979,001 describe a light sensitive material in which colloidal silver is incorporated to an emulsion layer or a layer adjacent thereto. However, although these patents surely realize the improvement in image quality, the following problems are still in need to be solved.
The color reversal photographic material is usually processed as follows.
An imagewise exposed color reversal photographic material is processed with a black-and-white negative developer called "first developer". The first developer usually contains a silver halide solvent such as rhodanate and sulfite and the development is a solution physical development. Then, silver halide grains which are neither exposed nor developed with the first developer are optically or chemically fogged and processed with a color developer called "second developer" to form a color positive image. Thereafter, the developed silver in the photographic material is bleached and fixed to provide a color reversal image.
In such a processing, it is well known that the solution physical development of light-sensitive silver halide grains at the first development is accelerated by adding silver halide with the light-insensitive surface or inside thereof being fogged or colloidal silver to a light-sensitive emulsion layer or a layer adjacent thereto. This means that the grain becomes susceptible to fluctuation in the rhodanate or sulfite content in the first developer, and this is verified in fact.
At city processing laboratories, the composition of developer is not always constant among laboratories and even in the same laboratory, the developer is in fact not controlled to have the composition in a constant range.
Accordingly, using the above-described photographic material greatly susceptible to the developer composition, a stable image can hardly be provided to users.
Under these circumstances, a photographic material capable of providing excellent image quality and processing stability has been demanded.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a silver halide color photographic material having superior. color reproducibility and good processing stability.
The above-described object has been achieved by:
(1) a silver halide color photographic material comprising a support having provided thereon at least one blue-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one red-sensitive emulsion layer, wherein at least one emulsion layer in any one of color-sensitive layers contains a silver halide grain having incorporated therein a rhodium ion and the emulsion layer or a layer adjacent to the emulsion layer contains a silver halide emulsion with at least one of the inside and/or surface of substantially light-insensitive grains being fogged or colloidal silver;
(2) the silver halide color photographic material as in item (1), wherein the layer containing a silver halide grain having incorporated therein a rhodium ion and containing a silver halide emulsion with at least one of the inside and/or surface of substantially light-insensitive grains being fogged or colloidal silver is the lowest-sensitivity emulsion layer in the color-sensitive layer, or the layer containing a silver halide emulsion with at least one of the inside and/or surface of substantially light-insensitive grains being fogged or colloidal silver is provided adjacent to the lowest-sensitivity emulsion layer in the color-sensitive layer;
(3) the silver halide color photographic material as in item (1), wherein the silver halide emulsion with at least one of the inside and/or surface of substantially light-insensitive grains being fogged or colloidal silver is colloidal silver having a maximum absorption wavelength of from 400 nm to 500 nm;
(4) the silver halide color photographic material as in item (1), wherein the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer each is composed of at least three emulsion layers having different sensitivities; and
(5) a method for forming a silver halide color photographic image comprising a processing of the silver halide color photographic material of items (1) to (4) with a developer containing thiocyanate.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described below in detail.
In the present invention, the layer containing a silver halide emulsion with at least one of the inside or the surface of substantially light-insensitive grains being fogged or colloidal silver is preferably provided adjacent to at least one of the blue-sensitive, green-sensitive and red-sensitive layers. If the silver halide emulsion with at least one of the inside or the surface of substantially light-insensitive grains being fogged or colloidal silver is incorporated into the high-sensitivity light-sensitive layer, the developer composition becomes of great influence and causes serious damage such as that the photographic material may undergo the formation of unnecessary fog during storage or development. On the other hand, if the silver halide emulsion with at least one of the inside or the surface of substantially light-insensitive grains being fogged or colloidal silver is incorporated into a layer not adjacent to a color-sensitive layer, for example, with an interlayer intervening therebetween, the color reproducibility is deteriorated.
In the present invention, when the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layers each is composed of two or more layers having different sensitivities or spectral sensitivities, the silver halide emulsion with at least one of the inside or the surface of substantially light-insensitive grains being fogged or colloidal silver is very preferably incorporated into the layer adjacent to the lowest-sensitivity layer of each color-sensitive layer.
The above-described effects can be very prominently exerted when the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer all are composed of three or more layers having different sensitivities.
The silver halide grain having incorporated therein a rhodium ion according to the present invention will be described below.
The rhodium ion is incorporated into the silver halide grain by introducing a rhodium complex (complex salt) thereinto during or after the formation of silver halide grain. The rhodium complex is trivalent rhodium and its ligands are not particularly restricted but at least one of the ligands is preferably bromine.
The above-described rhodium complex can be incorporated into the silver halide grain according to conventional methods. More specifically, at the time when a silver ion solution and an aqueous halogen solution are mixed with stirring to form silver halide grains, an aqueous solution having dissolved therein a complex used in the present invention (in the case when the formed silver halide grain contains bromine, a KBr solution in which the complex is present together may be used) is added to the above-described mixed reaction solution so that the rhodium ion is incorporated into the silver halide grain. Alternatively, the rhodium ion can be incorporated into the grain by adding an aqueous solution of the above-described complex to the reaction solution after the formation of silver halide grains. In this case, the ion may be covered by silver halide.
The amount of rhodium (content) is preferably from 10.sup.-9 to 10.sup.-2 mol, more preferably from 10.sup.-8 to 10.sup.-2 mol, per mol of silver halide.
Metals other than rhodium may be incorporated into the silver halide grain of the present invention. Examples of the metal include metals described in JP-A-1-14647 (e.g., Mn, Cu, Zn, Cd, Pb, Bi, In, Tl, Zr, La, Cr, Re or metals other than rhodium belonging to Group VIII in the Periodic Table). Two or more of these metals may be incorporated into the grain.
These metals can also be incorporated into the silver halide grain according to the same method as the above-described method for incorporating rhodium for use in the present invention. Depending upon the metal incorporated, an organic solvent may be partly used at the preparation of an aqueous solution of the metal. The method for incorporating metals into the silver halide grain is described in U.S. Pat. Nos. 3,761,276 and 4,395,478 and JP-A-59-216136.
The above-described metal which can be used in combination with rhodium is preferably present in the silver halide grain in an amount of from 10.sup.-9 to 10.sup.-2 mol, more preferably from 10.sup.-7 to 10.sup.-3 mol, per mol of silver halide.
The silver halide grain for use in the present invention may have a regular crystal form such as cubic, octahedral, dodecahedral or tetradecahedral form (see JP-A-2-223948) or an irregular crystal form such as sphere, or an emulsion described in JP-A-1-131547 and JP-A-1-158429 may also be used, in which tabular grains having an aspect ratio of 2 or more, particularly 8 or more, accounts for 50% or more of the total projected area of grains. Also, the grain may have a composite form of various crystals or an emulsion composed of a mixture thereof may be used.
The silver halide of the present invention preferably has a composition of silver bromide, silver chloride, silver chlorobromide, silver iodobromide or silver chloroiodobromide. The silver iodobromide is particularly preferred in the present invention.
The average grain size of silver halide grains (an average based on the projected area in the case of a sphere or nearly sphere grain, by taking the diameter and in the case of a cubic grain, the longitudinal length as a grain size) is preferably from 2.0 to 0.07 .mu.m, particularly preferably from 1.2 to 0.1 .mu.m. The grain size distribution may be either narrow or broad, however, a so-called "monodisperse" silver halide emulsion is preferably used for improving granularity or sharpness, which has a narrow grain size distribution such that 90% or more, particularly preferably 95% or more, by grain number or weight, of grains has a grain size within the average grain size .+-.40%, preferably .+-.30%, most preferably .+-.20%.
In order to achieve gradation which the photographic material intends to provide, a plurality of groups of grains each having different grain sizes may be mixed in the same layer or coated on separate layers in emulsion layers having substantially the same color sensitivity. Further, two or more polydisperse silver halide emulsions or combinations of a monodisperse emulsion and a polydisperse emulsion may be mixed in the same layer or coated on separate layers.
Now, the silver halide emulsion with at least one of the inside or the surface of substantially light-insensitive grains being fogged or colloidal silver for use in the present invention will be described in detail.
The silver halide grain with the surface and/or the inside thereof being fogged as used in the present invention means a silver halide grain adjusted by a chemical method or light such that the grain contains in the surface and/or the inside thereof a fogging nucleus and is developable irrespective of exposure.
The silver halide grain with the surface thereof being fogged (surface-fogged silver halide grain) can be prepared by fogging the silver halide grain by a chemical method or light during and/or after the formation of silver halide grain.
The above-described fogging process can be carried out under appropriate pH and pAg conditions, for example, by adding a reducing agent or a gold salt, by heating at a low pAg or by applying uniformexposure. Examples of the reducing agent include stannous chloride, a hydrazine-based compound, ethanolamine and thiourea dioxide.
The fogging by the addition of such a fogging material is preferably carried out before water washing so as to prevent the aging fog due to the diffusion of the fogging material to the light-sensitive emulsion layer.
The silver halide grain with the inside thereof being fogged (inside-fogged silver halide grain) can be prepared by forming a shell on the surface of the above-described surface-fogged silver halide grain used as a core. JP-A-59-214852 describes on such an inside-fogged silver halide grain in detail. The effects of the inside-fogged silver halide grain on sensitization development can be controlled by controlling the shell thickness.
The inside-surface silver halide grain can also be prepared by forming a fogged core according to the above-described fogging method from the starting of grain formation and then attaching an unfogged shell thereto. If desired, the grain may be fogged over all from the inside to the surface.
The fogged silver halide grain may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide but it is preferably silver bromide or silver iodobromide. The fogged silver halide grain preferably has an iodide content of 5 mol % or less, more preferably 2 mol % or less. The fogged silver halide grain may have a structure wherein the shell of the grain is different in the halogen composition from the core of the grain.
The average grain size of the fogged silver halide grain used in the present invention is not particularly limited, however, when the fogged silver halide grain is added to a light-sensitive silver halide emulsion layer or a light-insensitive layer, it is preferably smaller than the average grain size of silver halide grain in the lowest-sensitivity layer of the adjacent layer. Specifically, it is preferably 0.5 .mu.m or less, more preferably 0.2 .mu.m or less and most preferably 0.1 .mu.m or less.
The crystal form of the fogged silver halide grain is not particularly limited and the grain may be either regular grains or irregular grains. Also, the fogged silver halide grain may be polydisperse but it is preferably monodisperse.
The amount of the fogged silver halide grain used may be freely changed according to the degree of necessity in the present invention, however, in terms of the ratio to the entire amount of light-sensitive silver halide contained in all layers of the color photographic material of the present invention, it is preferably from 0.05 to 50 mol %, more preferably from 0.1 to 25 mol %. In view of the fogging efficiency per silver amount used, the surface fogged silver halide preferably has a smaller average grain size (specifically, 0.2 .mu.m or less).
The colloidal silver used in the present invention will be described below in detail.
The preparation for various types of colloidal silver are described, for example, in Weiser, Colloidal Elements, Wiley & Sons, New York, 1933 (yellow colloidal silver by Carey Lea's dextrin reduction method), German Patent No. 1,096,193 (brown and black colloidal silvers) and U.S. Pat. No. 2,688,601 (blue colloidal silver). Among these, yellow colloidal silver having a maximum absorption wavelength of from 400 to 500 nm is particularly preferred.
In the present invention, when the total amount of coated silver of the photographic material is 2 g/m.sup.2 or more, fabulous effects are achieved. If the total amount of coated silver is too large, the silver halide emulsion with at least one of the inside or the surface of substantially light-insensitive grains being fogged or colloidal silver cannot exert effects sufficiently and therefore, it is preferably from 3 to 6 g/m.sup.2, more preferably from 4 to 6 g/m.sup.2.
The silver halide emulsion with at least one of the inside or the surface of substantially light-insensitive grains being fogged or colloidal silver according to the present invention is coated on each layer preferably in an amount of from 0.001 to 0.4 g/m.sup.2, more preferably from 0.003 to 0.3 g/m.sup.2.
Various techniques and various inorganic and organic materials described in Research Disclosure No. 308119 (December, 1989) can be applied to the silver halide photographic emulsion and the silver halide photographic material using the same according to the present invention.
In addition, more specifically, for example, the techniques and inorganic/organic materials which can be used in the color photographic material to which the silver halide photographic emulsion according to the present invention is applied are described in the following portions of EP-A-436938 and in patents described below.
______________________________________Item Pertinent Portion______________________________________1) Layer structure from page 146, line 34 to page 147, line 252) Silver halide from page 147, line 26 to page emulsion 148, line 123) Yellow coupler from page 137, line 35 to page 146, line 33 and page 149, lines 21 to 234) Magenta coupler page 149, lines 24 to 28; EP-A- 421453, from page 3, line 5 to page 25, line 555) Cyan coupler page 149, lines 29 to 33; EP-A- 432804, from page 3, line 28 to page 40, line 26) Polymer coupler page 149, lines 34 to 38; EP-A- 435334, from page 113, line 39 to page 123, line 377) Colored coupler from page 53, line 42 to page 137, line 34 and page 149, lines 39 to 458) Other functional from page 7, line 1 to page 53, couplers line 41 and from page 149, line 46 to page 150, line 3; EP-A- 435334, from page 3, line 1 to page 29, line 509) Antiseptic/antimold page 150, lines 25 to 2810) Formalin scavenger page 149, lines 15 to 1711) Other additives page 153, lines 38 to 47; EP-A- 421453, from page 75, line 21 to page 84, line 56 and from page 27, line 40 to page 37, line 4012) Dispersion method page 150, lines 4 to 2413) Support page 150, lines 32 to 3414) Film thickness/ page 150, lines 35 to 49 physical properties15) Color development/ from page 150, line 50 to page black-and-white 151, line 47; EP-A-442323, page development, fogging 34, lines 11 to 54 and page 35, lines 14 to 2216) Desilvering from page 151, line 48 to page 152, line 5317) Automatic developer from page 152, line 54 to page 153, line 218) Water washing/ page 153, lines 3 to 37 stabilization______________________________________

The present invention will now be illustrated in greater detail by reference to the following example. However, the present invention should not to be construed as being limited to the example. Additionally, in the following example, all parts, percents or the like are by weight unless otherwise indicated.
EXAMPLE
Preparation of Sample 101:
A multilayer color photographic material was prepared to have the layers each having the following composition on a 127 .mu.m-thick cellulose triacetate film support having a subbing layer and designated as Sample 101. The numerals indicate the addition amount per m.sup.2. The effects of compounds added are not restricted to those described herein.
______________________________________First Layer: Antihalation LayerBlack colloidal silver 0.30 gGelatin 2.20 gUltraviolet ray absorbent U-1 0.10 gUltraviolet ray absorbent U-3 0.05 gUltraviolet ray absorbent U-4 0.10 gHigh boiling point organic solvent 0.30 gOil-1Fine crystal solid dispersion of 0.10 gDye E-1Second Layer: InterlayerGelatin 0.40 gCompound Cpd-I 7 mgCompound Cpd-J 3 mgCompound Cpd-K 3 mgHigh boiling point organic solvent 0.10 gOil-3Dye D-4 9 mgThird Layer: InterlayerGelatin 0.40 gFourth Layer: Low-sensitivity Red-sensitive Emulsion LayerEmulsion A.sub.1 as silver 0.30 gGelatin 0.60 gCoupler C-1 0.05 gCoupler C-2 0.15 gCoupler C-3 0.05 gCompound Cpd-C 5 mgCompound Cpd-J 5 mgHigh boiling point organic solvent 0.10 gOil-2Additive P-1 0.10 gFifth Layer: Middle-sensitivity Red-sensitive Emulsion LayerEmulsion B as silver 0.40 gEmulsion C as silver 0.10 gGelatin 1.50 gCoupler C-1 0.10 gCoupler C-2 0.30 gCoupler C-3 0.10 gHigh boiling point organic solvent 0.20 gOil-2Additive P-1 0.10 gSixth Layer: High-sensitivity Red-sensitivity Emulsion LayerEmulsion D as silver 0.25 gEmulsion E as silver 0.25 gGelatin 1.00 gCoupler C-1 0.15 gCoupler C-2 0.40 gCoupler C-3 0.15 gCoupler C-9 0.10 gAdditive P-1 0.10 gSeventh Layer: InterlayerGelatin 1.40 gAdditive M-1 0.30 gColor mixing inhibitor Cpd-I 0.03 gDye D-5 5 mgCompound Cpd-J 5 mgHigh boiling point organic solvent 0.02 gOil-1Eighth Layer: InterlayerGelatin 1.20 gAdditive P-1 0.20 gColor mixing inhibitor Cpd-A 0.10 gCompound Cpd-C 0.10 gNinth Layer: Low-sensitivity Green-sensitive Emulsion LayerEmulsion F.sub.1 as silver 0.30 gGelatin 0.70 gCoupler C-4 0.05 gCoupler C-11 0.10 gCoupler C-7 0.05 gCoupler C-8 0.10 gCompound Cpd-B 0.03 gCompound Cpd-D 0.02 gCompound Cpd-E 0.02 gCompound Cpd-F 0.04 gCompound Cpd-J 10 mgCompound Cpd-L 0.02 gHigh boiling point organic solvent 0.10 gOil-1High boiling point organic solvent 0.10 gOil-2Tenth Layer: Middle-sensitivity Green-sensitive Emulsion LayerEmulsion G as silver 0.40 gEmulsion H as silver 0.10 gGelatin 0.60 gCoupler C-4 0.05 gCoupler C-11 0.15 gCoupler C-7 0.05 gCoupler C-8 0.10 gCompound Cpd-B 0.03 gCompound Cpd-D 0.02 gCompound Cpd-E 0.02 gCompound Cpd-F 0.05 gCompound Cpd-L 0.05 gHigh boiling point organic solvent 0.05 gOil-2Eleventh Layer: High-sensitivity Green-sensitive Emulsin LayerEmulsion I as silver 0.45 gEmulsion J as silver 0.40 gGelatin 1.40 gCoupler C-4 0.15 gCoupler C-11 0.20 gCoupler C-7 0.10 gCoupler C-8 0.20 gCompound Cpd-B 0.03 gCompound Cpd-E 0.02 gCompound Cpd-F 0.04 gCompound Cpd-K 5 mgCompound Cpd-L 0.02 gHigh boiling point organic solvent 0.05 gOil-1High boiling point organic solvent 0.05 gOil-2Twelfth Layer: InterlayerGelatin 0.30 gCompound Cpd-L 0.05 gHigh boiling point organic solvent 0.05 gOil-1Thirteenth Layer: Yellow Filter LayerYellow colloidal silver as silver 0.10 gGelatin 0.90 gColor mixing inhibitor Cpd-A 0.01 gCompound Cpd-L 0.01 gHigh boiling point organic solvent 0.01 gOil-1Fine crystal solid dispersion of 0.05 gDye E-2Fourteenth Layer: InterlayerGelatin 0.6 gFifteenth Layer: Low-sensitivity Blue-sensitive Emulsion LayerEmulsion K.sub.1 as silver 0.4 gGelatin 1.40 gCoupler C-5 0.20 gCoupler C-6 0.10 gCoupler C-10 0.10 gSixteenth Layer: Middle-sensitivity Blue-sensitive Emulsion LayerEmulsion L as silver 0.15 gEmulsion M as silver 0.10 gGelatin 0.90 gCoupler C-5 0.20 gCoupler C-6 0.05 gCoupler C-10 0.10 gSeventeenth Layer: High-sensitivity Blue-sensitive EmulsionLayerEmulsion M as silver 0.10 gEmulsion N as silver 0.15 gEmulsion O as silver 0.20 gGelatin 1.50 gCoupler C-5 0.35 gCoupler C-6 0.10 gCoupler C-10 0.60 gHigh boiling point organic solvent 0.10 gOil-2Eighteenth Layer: First Protective LayerGelatin 1.70 gUltraviolet ray absorbent U-1 0.20 gUltraviolet ray absorbent U-2 0.05 gUltraviolet ray absorbent U-5 0.30 gFormalin scavenger Cpd-H 0.40 gDye D-1 0.15 gDye D-2 0.05 gDye D-3 0.10 gNineteenth Layer: Second Protective LayerColloidal silver as silver 0.1 mgFine grain silver as silver 0.10 giodobromide emulsion(average grain size: 0.06 .mu.m,AgI content: 1 mol %)Gelatin 0.60 gTwentieth Layer: Third Protective LayerGelatin 1.30 gPolymethyl methacrylate 0.10 g(average grain size: 1.5 .mu.m)Copolymer of methyl methacrylate 0.10 gand acrylic acid (4:6)(average grain size: 1.5 .mu.m)Silicone oil 0.03 gSurfactant W-1 3.0 mgSurfactant W-2 0.03 g______________________________________
The colloidal silver used in the nineteenth layer was prepared in the same manner as in the present invention. However, the nineteenth layer is not a layer adjacent to any emulsion layer containing a silver halide grain having incorporated therein a rhodium ion. Accordingly, Sample 101 falls outside the scope of the present invention.
In addition to the above-described composition, additives F-1 to F-8 were added to each emulsion layer. Also, in addition to the above-described composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating or emulsification were added to each layer.
Further, phenol, 1,2-benzisothiazoline-3-one, 2-phenoxyethanol, phenetyl alcohol or p-butyl benzoate were added as an antiseptic or an antimold.
TABLE 1__________________________________________________________________________Silver Iodobromide Emulsion used in Sample 101 Sphere-corresponding Coefficient of AgI Average Grain size Fluctuation ContentEmulsion Characteristics of Grain (.mu.m) (%) (%)__________________________________________________________________________.sub. A.sub.1 monodisperse cubic grain 0.10 11 4.5B monodisperse cubic grain 0.19 14 4.5C monodisperse cubic grain 0.31 16 4.5D polydisperse tabular grain, 0.60 28 4.5 average aspect ratio: 6.0E polydisperse tabular grain, 0.90 29 4.5 average aspect ratio: 6.3.sub. F.sub.1 monodisperse cubic grain 0.10 11 2.0G monodisperse cubic grain 0.18 14 4.7H monodisperse cubic grain 0.40 17 4.7I polydisperse tabular grain, 0.65 25 4.0 average aspect ratio: 6.0J monodisperse tabular grain, 1.05 18 3.0 average aspect ratio: 4.5.sub. K.sub.1 monodisperse cubic grain 0.15 15 2.0L monodisperse cubic grain 0.20 17 2.0M monodisperse cubic grain 0.34 17 2.0N polydisperse tabular grain, 0.65 28 2.0 average aspect ratio: 6.0O polydisperse internal high 1.70 33 2.0 iodide-type twin crystal grain__________________________________________________________________________
TABLE 2______________________________________Spectral Sensitization of Emulsions A to O Addition Amount per mol of SilverEmulsion Sensitizing Dye Added Halide (g)______________________________________.sub. A.sub.1 S-1 0.30 S-2 0.10B S-1 0.26 S-2 0.26C S-1 0.24 S-2 0.24D S-1 0.15 S-2 0.15E S-1 0.11 S-2 0.03.sub. F.sub.1 S-3 0.97G S-3 0.50H S-3 0.36I S-3 0.43J S-3 0.36.sub. K.sub.1 S-4 0.30L S-4 0.28M S-4 0.14N S-4 0.21O S-4 0.27______________________________________ ##STR1## Preparation of Samples 102 to 125:
Samples 102 to 125 were prepared in the same manner as Sample 101 except for using Emulsions A.sub.2, F.sub.2 and K.sub.2 each having incorporated therein an Rh ion in place of Emulsions A, F and K.sub.1 used in Sample 101 and using a fogged emulsion and yellow colloidal silver (maximum absorption wavelength: 450 nm). The characteristics of Emulsions A.sub.2, F.sub.2 and K.sub.2, the fogged emulsion and the yellow colloidal silver are shown in Table 3 and the characteristics of Samples 102 to 125 are shown in Table 4.
TABLE 3__________________________________________________________________________Characteristics of Emulsions A.sub.2, F.sub.2 and K.sub.2, FoggedEmulsion X and Yellow Colloidal Silver Y Coefficient of size Fluctuation Rh Ion Sensitizing DyeEmulsion (.mu.m) (%) (mol/mol-Ag) (g/mol-Ag) Remarks__________________________________________________________________________.sub. A.sub.2 0.18 12 3.6 .times. 10.sup.-7 S-1 0.17 AgI content was the same as in S-2 0.06 Emulsion A.sub.1.sub. F.sub.2 0.18 12 3.6 .times. 10.sup.-7 S-3 0.54 AgI content was the same as in Emulsion F.sub.1.sub. K.sub.2 0.25 18 3.6 .times. 10.sup.-7 S-4 0.18 AgI content was the same as in Emulsion K.sub.1X 0.06 13 none none fine grained silver iodobromide emulsion with the surface and the inside thereof being fogged, AgI content: 1 mol %Y -- -- none none yellow colloidal silver, AgI content: 1.0 mol %__________________________________________________________________________
TABLE 4__________________________________________________________________________ Thir-Third Fourth Layer Eight Ninth Layer teenth Fifteenth Layer Layer, Emulsion Layer, Emulsion Layer, Fourteenth Emulsion X or Y A.sub.1 or A.sub.2 X or Y X or Y F.sub.1 or F.sub.2 X or Y Y Layer, K.sub.1 or X or Y2Sample (g/m.sup.2) (g/m.sup.2) (g/m.sup.2) (g/m.sup.2) (g/m.sup.2) (g/m.sup.2) (g/m.sup.2) Interlayer (g/m.sup.2) (g/m.sup.2) Remarks__________________________________________________________________________101 none A.sub.1 (0.30) none none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Comparison102 none A.sub.1 (0.30) none none F.sub.1 (0.30) none (0.30) omitted K.sub.1 (0.40) none Comparison103 none A.sub.1 (0.30) none none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) Y (0.008) Comparison104 none A.sub.1 (0.30) none none F.sub.1 (0.30) none (0.30) omitted K.sub.2 (0.40) none Invention105 none A.sub.1 (0.30) none none F.sub.1 (0.30) none (0.30) provided K.sub.2 (0.40) Y (0.008) Invention106 none A.sub.1 (0.30) none X (0.05) F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Comparison107 none A.sub.1 (0.30) none Y (0.05) F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Comparison108 none A.sub.1 (0.30) none none F.sub.1 (0.30) X (0.006) (0.30) provided K.sub.1 (0.40) none Comparison109 none A.sub.1 (0.30) none none F.sub.1 (0.30) Y (0.006) (0.30) provided K.sub.1 (0.40) none Comparison110 none A.sub.1 (0.30) none X (0.05) F.sub.2 (0.30) none (0.30) provided K.sub.1 (0.40) none Invention111 none A.sub.1 (0.30) none Y (0.05) F.sub.2 (0.30) none (0.30) provided K.sub.1 (0.40) none Invention112 none A.sub.1 (0.30) none none F.sub.2 (0.30) X (0.006) (0.30) provided K.sub.1 (0.40) none Invention113 none A.sub.1 (0.30) none none F.sub.2 (0.30) Y (0.006) (0.30) provided K.sub.1 (0.40) none Invention114 X (0.05) A.sub.1 (0.30) none none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Comparison115 Y (0.05) A.sub.1 (0.30) none none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Comparison116 none A.sub.1 (0.30) X (0.006) none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Comparison117 none A.sub.1 (0.30) Y (0.006) none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Comparison118 X (0.05) A.sub.2 (0.30) none none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Invention119 Y (0.05) A.sub.2 (0.30) none none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Invention120 none A.sub.2 (0.30) X (0.006) none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Invention121 none A.sub.2 (0.30) Y (0.006) none F.sub.1 (0.30) none (0.30) provided K.sub.1 (0.40) none Invention122 X (0.05) A.sub.2 (0.30) none X (0.05) F.sub.2 (0.30) none (0.30) omitted K.sub.2 (0.40) none Invention123 Y (0.05) A.sub.2 (0.30) none Y (0.05) F.sub.2 (0.30) none (0.30) omitted K.sub.2 (0.40) none Invention124 none A.sub.2 (0.30) X (0.006) none F.sub.2 (0.30) Y (0.006) (0.30) provided K.sub.2 (0.40) Y (0.008) Invention125 Y (0.05) A.sub.2 (0.30) none Y (0.05) F.sub.2 (0.30) none (0.30) omitted K.sub.2 (0.40) none Invention__________________________________________________________________________
A plurality of strips were cut from the thus prepared Samples 101 to 125, wedgewise exposed through optical wedge using a halogen lamp having color temperature of 3200.degree. K. as a light source and processed with the following standard color reversal developer (First Developer FD-S). Each strip was subjected to sensitometry with respect to each of cyan, magenta and yellow images. Further, for testing the processing stability, four strips cut from Samples 101 to 125 were wedgewise exposed in the same manner as above and processed with Developer FD-1, FD-2, FD-3 or FD-4 which was prepared from the first developer as a standard processing solution in the above-described color reversal processing by changing the amount of potassium thiocyanate and the amount of sodium sulfite as shown in Table 5. These strips were also subjected to sensitometry in the same manner as above. The results obtained are shown in Table 6.
TABLE 5______________________________________ FD-S FD-1 FD-2 FD-3 FD-4Name of Chemicals (g) (g) (g) (g) (g)______________________________________Potassium thiocyanate 1.2 0.8 1.6 1.2 1.2Sodium sulfite 30 30 30 20 40______________________________________
TABLE 6__________________________________________________________________________Processing Stability__________________________________________________________________________Cyan Image Magenta ImageFD-1 FD-2 FD-3 FD-4 FD-1 FD-2 FD-3 FD-4Sample .DELTA.S.sub.1 .DELTA.S.sub.2 .vertline..DELTA.S.sub.1 /.DELTA.S.sub.2 .vertline. .DELTA.S.sub.3 .DELTA.S.sub.4 .vertline..DELTA.S.sub.3 /.DELTA.S.sub.4 .vertline. .DELTA.S.sub.1 .DELTA.S.sub.2 .vertline..DELTA.S.sub.1 /.DELTA.S. sub.2 .vertline. .DELTA.S.sub.3 .DELTA.S.sub.4 .vertline..DELTA.S.sub .3 /.DELTA.S.sub.4 .vertline.__________________________________________________________________________101 -0.25 0.20 1.25 -0.20 0.16 1.25 -0.23 0.18 1.28 -0.18 0.14 1.29102 -0.25 0.20 1.25 -0.25 0.20 1.25 -0.24 0.20 1.20 -0.19 0.16 1.19103 -0.25 0.20 1.25 -0.26 0.21 1.24 -0.24 0.21 1.14 -0.19 0.16 1.19104 -0.25 0.20 1.25 -0.24 0.20 1.20 -0.22 0.18 1.22 -0.17 0.14 1.21105 -0.25 0.20 1.25 -0.25 0.20 1.25 -0.22 0.17 1.29 -0.18 0.14 1.29106 -0.26 0.20 1.30 -0.21 0.17 1.24 -0.28 0.30 0.93 -0.26 0.21 1.24107 -0.26 0.21 1.24 -0.22 0.17 1.29 -0.30 0.35 0.86 -0.29 0.27 1.07108 -0.27 0.21 1.24 -0.21 0.18 1.17 -0.29 0.31 0.94 -0.28 0.22 1.27109 -0.26 0.21 1.24 -0.22 0.18 1.22 -0.31 0.36 0.86 -0.31 0.27 1.15110 -0.23 0.19 1.21 -0.19 0.16 1.19 -0.15 0.15 1.00 -0.13 0.12 1.08111 -0.24 0.19 1.26 -0.18 0.15 1.20 -0.16 0.15 1.07 -0.14 0.14 1.00112 -0.23 0.20 1.15 -0.19 0.17 1.12 -0.16 0.16 1.00 -0.14 0.12 1.17113 -0.24 0.20 1.20 -0.19 0.16 1.19 -0.17 0.16 1.06 -0.15 0.14 1.07114 -0.33 0.39 0.85 -0.27 0.31 0.87 -0.24 0.19 1.26 -0.19 0.16 1.19115 -0.35 0.43 0.81 -0.31 0.23 1.35 -0.25 0.20 1.25 -0.20 0.16 1.25116 -0.34 0.40 0.85 -0.30 0.34 0.88 -0.24 0.20 1.20 -0.20 0.18 1.11117 -0.36 0.45 0.80 -0.33 0.35 0.94 -0.26 0.21 1.24 -0.21 0.17 1.24118 -0.18 0.19 0.95 -0.16 0.17 0.94 -0.22 0.17 1.29 -0.17 0.16 1.06119 -0.19 0.19 1.00 -0.17 0.17 1.00 -0.21 0.17 1.24 -0.17 0.13 1.31120 -0.20 0.19 1.05 -0.17 0.18 0.94 -0.22 0.18 1.22 -0.18 0.16 1.13121 -0.21 0.19 1.11 -0.18 0.18 1.00 -0.22 0.19 1.16 -0.18 0.15 1.20122 -0.18 0.19 0.95 -0.16 0.16 1.00 -0.15 0.15 1.00 -0.13 0.13 1.00123 -0.18 0.19 0.95 -0.16 0.16 1.00 -0.16 0.15 1.07 -0.14 0.13 1.08124 -0.20 0.19 1.05 -0.16 0.17 0.94 -0.16 0.16 1.00 -0.15 0.15 1.00125 -0.19 0.19 1.00 -0.17 0.17 1.00 -0.16 0.16 1.00 -0.14 0.14 1.00__________________________________________________________________________ Yellow Image FD-1 FD-2 FD-3 FD-4 Sample .DELTA.S.sub.1 .DELTA.S.sub.2 .vertline..DELTA.S.sub.1 /.DELTA.S.sub.2 .vertline. .DELTA.S.sub.3 .DELTA.S.sub.4 .vertline..DELTA.S.sub.3 /.DELTA.S.sub.4 .vertline. Remarks__________________________________________________________________________ 101 -0.31 0.25 1.24 -0.24 0.19 1.26 Comparison 102 -0.33 0.41 0.80 -0.26 0.28 0.93 Comparison 103 -0.34 0.43 0.79 -0.28 0.29 0.97 Comparison 104 -0.22 0.22 1.00 -0.17 0.16 1.06 Invention 105 -0.21 0.22 0.95 -0.17 0.17 1.00 Invention 106 -0.32 0.25 1.28 -0.24 0.20 1.20 Comparison 107 -0.33 0.26 1.27 -0.25 0.22 1.14 Comparison 108 -0.33 0.25 1.32 -0.24 0.21 1.14 Comparison 109 -0.34 0.27 1.26 -0.26 0.22 1.18 Comparison 110 -0.31 0.26 1.19 -0.24 0.20 1.20 Invention 111 -0.32 0.26 1.23 -0.25 0.20 1.25 Invention 112 -0.32 0.26 1.23 -0.25 0.20 1.25 Invention 113 -0.33 0.27 1.22 -0.25 0.20 1.25 Invention 114 -0.31 0.25 1.24 -0.24 0.19 1.26 Comparison 115 -0.31 0.25 1.24 -0.24 0.19 1.26 Comparison 116 -0.31 0.26 1.19 -0.24 0.19 1.26 Comparison 117 -0.32 0.26 1.23 -0.24 0.19 1.26 Comparison 118 -0.31 0.25 1.24 -0.24 0.19 1.26 Invention 119 -0.31 0.25 1.24 -0.24 0.19 1.26 Invention 120 -0.31 0.25 1.24 -0.24 0.19 1.26 Invention 121 -0.31 0.25 1.24 -0.24 0.19 1.26 Invention 122 -0.21 0.22 0.95 -0.17 0.16 1.06 Invention 123 -0.21 0.22 0.95 -0.17 0.16 1.06 Invention 124 -0.22 0.23 0.97 -0.17 0.17 1.00 Invention 125 -0.22 0.22 1.00 -0.17 0.17 1.00 Invention__________________________________________________________________________ Note 1: .DELTA.S.sub.1 to .DELTA.S.sub.4 each means the difference in log values of the exposure amount (CMS unit) to give the minimum density + 0. for each image between the processing with First Developer FD1, FD2, FD3 or FD4 and the processing with standard First Developer FDS. Note 2: .vertline..DELTA.S.sub.1 /.DELTA.S.sub.2 .vertline. and .vertline..DELTA.S.sub.3 /.DELTA.S.sub.4 .vertline. represent an absolute value of the ratio of .DELTA.S.sub.1 to .DELTA.S.sub.2 and an absolute value of the ratio of .DELTA.S.sub.3 to .DELTA.S.sub.4, respectively.
Standard Processing
______________________________________ Tank Replenishing Time Temp. Volume AmountProcessing (min.) (.degree.C.) (l) (ml/m.sup.2)______________________________________First development 6 38 12 2,200First washing 2 38 4 7,500Reversal 2 38 4 1,100Color development 6 38 12 2,200Prebleaching 2 38 4 1,100Bleaching 6 38 12 220Fixing 4 38 8 1,100Second washing 4 38 8 7,500Final rinsing 1 25 2 1,100______________________________________
Each processing solution had the following composition.
______________________________________ Tank Solution ReplenisherFirst Developer (FD-S) (g) (g)______________________________________Pentasodium nitrilo-N,N,N- 1.5 1.5trimethylene phosphonatePentasodium diethylenetri- 2.0 2.0aminepentaacetateSodium sulfite 30 30Potassium hydroquinone 20 20monosulfonatePotassium carbonate 15 20Potassium bicarbonate 12 151-Phenyl-4-methyl-4- 1.5 2.0hydroxymethyl-3-pyrazolidonePotassium bromide 2.5 1.4Potassium thiosulfate 1.2 1.2Potassium iodide 2.0 mg --Diethylene glycol 13 15Water to make 1,000 ml 1,000 mlpH 9.60 9.60______________________________________
pH was adjusted with sulfuric acid or potassium hydroxide.
______________________________________ Tank Solution ReplenisherReversal Solution (g) (g)______________________________________Pentasodium nitrilo-N,N,N- 3.0 same as tanktrimethylene phosphonate solutionStannous chloride dihydrate 1.0p-Aminophenol 0.1Sodium hydroxide 8Glacial acetic acid 15 mlWater to make 1,000 mlpH 6.00______________________________________
pH was adjusted with acetic acid or sodium hydroxide.
______________________________________ Tank Solution ReplenisherColor developer (g) (g)______________________________________Pentasodium nitrilo-N,N,N- 2.0 2.0trimethylene phosphonateSodium sulfite 7.0 7.0Trisodium phosphate 36 36dodecahydratePotassium bromide 1.0 --Potassium iodide 90 mg --Sodium hydroxide 3.0 3.0Citrazinic acid 1.5 1.5N-Ethyl-N-(.beta.-methanesulfon- 11 11amidoethyl)-3-methyl-4-aminoaniline 3/2 sulfatemonohydrate3,6-Dithiaoctane-1,8-diol 1.0 1.0pH 11.86 12.00______________________________________
pH was adjusted with hydrochloric acid or sodium hydroxide.
______________________________________ Tank Solution ReplenisherPrebleaching Solution (g) (g)______________________________________Disodium ethylenediamine- 8.0 8.0tetraacetate dihydrateSodium sulfite 6.0 8.01-Thioglycerol 0.4 0.4Formaldehyde sodium 30 35bisulfite adductWater to make 1,000 ml 1,000 mlpH 6.30 6.10______________________________________
pH was adjusted with acetic acid or sodium hydroxide.
______________________________________ Tank Solution ReplenisherBleaching Solution (g) (g)______________________________________Disoduim ethylenediamine- 2.0 4.0tetraacetate dihydrateAmmonium ethylenediamine- 120 240tetraacetato ferrate dihydratePotassium bromide 100 200Ammonium nitrate 10 20Water to make 1,000 ml 1,000 mlpH 5.70 5.50______________________________________
pH was adjusted with nitric acid or sodium hydroxide.
______________________________________Fixing Solution______________________________________Ammonium thiosulfate 80 gSodium sulfite 5.0 gSodium bisulfite 5.0 gWater to make 1,000 mlpH 6.60______________________________________
pH was adjusted with acetic acid or aqueous ammonia.
______________________________________Stabilizing Solution______________________________________Formalin (37%) 5.0 mlPolyoxyethylene-p-monononyl- 0.5 mlphenyl ether (polymerizationdegree: 10)Water to make 1,000 ml______________________________________
In order to compare the color reproducibility of each sample to the transparent original, the same transparent original was printed on each sample. The transparent original used was a color slide obtained from a Fuji chrome professional reversal film (RDP, produced by Fuji Photo Film Co., Ltd.).
Color differences were examined on the points in a definite straight line section of the original and in the corresponding definite straight line section of each print and values on several representative points are shown in Table 7. The color differences used were color differences by L*a*b* chromaticity diagram.
In Table 7, color differences on the determination points a to g of each sample corresponding to the determination points a to g of the transparent original are shown. In these determination points, the following images are printed in practice.
a: black background, b: gray chart, c: red flower petal, d: leaf, e: blue book, f: highlight portion of a face, and g: shadow portion of a face.
TABLE 7______________________________________Color ReproducibilityColor Difference(smaller value indicatesbetter color reproducibility)Sample a b c d e f g Remarks______________________________________101 5.3 6.1 11.4 13.7 9.8 5.3 4.7 Comparison102 3.8 5.5 10.1 12.8 5.3 3.8 2.5 Comparison103 3.9 5.5 10.2 12.8 5.4 4.0 2.6 Comparison104 3.9 5.4 10.3 12.9 5.8 4.0 2.6 Invention105 4.0 5.5 10.3 13.0 5.7 4.1 2.7 Invention106 3.7 5.4 10.2 8.4 7.7 3.9 2.5 Comparison107 3.4 5.1 9.9 7.9 7.4 3.8 2.3 Comparison108 3.8 5.3 10.1 8.6 7.6 3.7 2.6 Comparison109 3.5 5.1 10.0 8.2 7.5 3.9 2.4 Comparison110 3.8 5.5 10.4 8.7 7.9 4.0 2.6 Invention111 3.5 5.2 10.0 8.1 7.6 3.9 2.4 Invention112 3.7 5.6 10.1 8.5 7.7 3.9 2.5 Invention113 3.6 5.3 10.1 8.2 7.8 3.8 2.5 Invention114 3.7 5.5 8.3 11.8 7.8 4.9 3.8 Comparison115 3.5 5.3 7.9 11.5 7.5 4.7 3.5 Comparison116 3.6 5.4 8.2 11.7 7.9 5.0 3.9 Comparison117 3.5 5.4 8.0 11.4 7.6 4.9 3.6 Comparison118 3.8 5.6 8.4 12.0 7.9 5.1 2.8 Invention119 3.6 5.5 8.1 11.6 7.7 3.8 2.5 Invention120 3.8 5.7 8.3 12.1 7.8 5.0 2.7 Invention121 3.6 5.6 8.1 11.7 7.8 3.7 2.6 Invention122 2.3 5.0 7.6 8.0 6.0 3.1 2.8 Invention123 1.7 3.8 7.4 7.7 5.1 2.6 2.5 Invention124 1.5 2.7 7.1 7.6 4.8 2.6 2.4 Invention125 1.4 2.6 7.0 7.4 4.7 2.5 2.3 Invention______________________________________
From Tables 6 and 7, it is seen that as compared with Sample 101, Samples 102, 103, 106 to 109 and 114 to 117 has superior color reproducibility however underwent deterioration in processing stability. On the other hand, samples of the present invention exhibited superior color reproducibility and at the same time good processing stability. Further, upon comparison between samples 110 and 111, between samples 112 and 113, between samples 118 and 119 and between 120 and 121, still better color reproducibility could be achieved by using yellow colloidal silver.
In conclusion, samples of the present invention can be said to provide superior color reproducibility and good processing stability.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Number	Name	Date
T979001	Graham	Feb 1979
4617259	Ogawa et al.	Oct 1986
4626498	Shuto et al.	Dec 1986
4814263	Hine	Mar 1989
4933272	McDugle et al.	Jun 1990
5206132	Mitsuhashi	Apr 1993
5437968	Nagaoka	Aug 1995

Number	Date	Country
60-126652	Jun 1985	JPX
2110539	Apr 1990	JPX
3226732	Oct 1991	JPX

Silver halide color photographic material

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