Silver halide color photographic light-sensitive material

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a silver halide color photographic light-sensitive material and, more particularly, to a silver halide color photographic light-sensitive material which has a good color reproduction and also has a high speed and a high graininess.
2. Description of the Related Art
Conventionally, the use of an interlayer inhibiting effect (interlayer effect) is known as means of improving color reproduction in silver halide color photographic light-sensitive materials.
In the case of color negative light-sensitive materials, by allowing a green-sensitive layer to have a development inhibiting effect on a red-sensitive layer, the color formation of the red-sensitive layer in white exposure can be suppressed to be lower than that in red exposure. Likewise, a development inhibiting effect that the red-sensitive layer has on the green-sensitive layer can yield the reproduction of green with a high saturation.
If, however, the saturations of three primary colors, red, green, and blue, are increased by using these methods, hues from yellow to cyan green lose their fidelities, and so the technique described in JP-A-61-34541 ("JP-A" means Published Unexamined Japanese Patent Application) has been proposed as a countermeasure. This technique aims to achieve a fresh, high-fidelity color reproduction in a silver halide color light-sensitive material comprising a support having provided thereon at least one blue-sensitive silver halide emulsion layer containing a color coupler for forming a yellow color, at least one green-sensitive silver halide emulsion layer containing a color coupler for forming a magenta color, and at least one red-sensitive silver halide emulsion layer containing a color coupler for forming a cyan color, wherein the barycentric sensitivity wavelength (barycenter .lambda..sub.G l) of the spectral sensitivity distribution of the green-sensitive layer is 520 nm.ltoreq.barycenter .lambda..sub.G .ltoreq.580 nm, the barycentric wavelength (barycenter .lambda..sub.-R) of the distribution of magnitudes of an interlayer effect which a given layer has on at least one red-sensitive silver halide emulsion layer at a wavelength ranging from 500 nm to 600 nm is 500 nm<barycenter .lambda..sub.-R .ltoreq.600 nm, and barycentric input .sub.G -barycenter .lambda..sub.-R .ltoreq.5 nm.
When, however, photography was performed by using light-sensitive materials manufactured as described above and the consequent color prints were evaluated, it was found that the graininess of the silver halide emulsion layer having the interlayer effect on the red-sensitive layer was lower than those of the other color-sensitive layers.
The reason for this is estimated that the absorption of sensitizing dyes conventionally used is weak in the layer with the interlayer effect and a yellow filter layer cuts more light around 500 nm than is necessary.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material which has a good color reproduction and also has a high speed and a high graininess.
The above object of the present invention is achieved by the following means.
A silver halide color photographic light-sensitive material comprising a support having provided thereon at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, at least one red-sensitive silver halide emulsion layer, and at least one hydrophilic colloid layer, wherein the hydrophilic colloid layer contains a compound represented by Formula (I) below, a silver halide emulsion layer having an interlayer effect on the red-sensitive layer is also provided, and the layer with the interlayer effect contains a silver halide emulsion spectrally sensitized with a sensitizing dye represented by Formula (II) or (III) below. ##STR2##
In this Formula (I), R.sub.1 represents a hydrogen atom, alkyl, alkenyl, aryl, a heterocyclic ring, ureido, sulfonamide, sulfamoyl, sulfonyl, sulfinyl, alkylthio, arylthio, oxycarbonyl, acyl, carbamoyl, cyano, alkoxy, aryloxy, amino, or amide, and Q represents --O-- or --NR.sub.2 -wherein R.sub.2 represents a hydrogen atom, alkyl, aryl, or a heterocyclic group.
R.sub.3, R.sub.4, and R.sub.5 each represent a hydrogen atom, alkyl, or aryl, and R.sub.4 and R.sub.5 may be bonded to each other to form a 6-membered ring.
R.sub.6 represents a hydrogen atom, alkyl, aryl, or amino.
L.sub.1, L.sub.2, and L.sub.3 each represent methine, and k is an integer of 0 or 1. ##STR3##
In this Formula (II), R.sub.11, R.sub.12, R.sub.13, and R.sub.14 may be the same or different and each represent a hydrogen atom, a halogen atom, alkyl, aryl, alkoxy, aryloxy, aryloxycarbonyl, alkoxycarbonyl, amino, acyl, cyano, carbamoyl, sulfamoyl, carboxyl, or an acyloxy group.
R.sub.11 and R.sub.12 or R.sub.13 and R.sub.14 do not represent a hydrogen atom simultaneously.
R.sub.15 and R.sub.16 may be the same or different and each represent an alkyl group.
R.sub.17 represents an alkyl having three or more carbon atoms, aryl, or aralkyl group.
X.sub.1 represents a counter anion, and m is an integer of 0 or 1, and m=0 when intramolecular salt is to be formed. ##STR4##
In this Formula (III), R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, and R.sub.30 each have the same meaning as that of R.sub.11, R.sub.31 and R.sub.32 each have the same meaning as that of R.sub.15.
Y represents a sulfur atom, a selenium atom, or an oxygen atom, X.sub.2 has the same meaning as that of X.sub.1, and n has the same meaning as that of m.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in more detail below.
The light-sensitive material of the present invention is a color light-sensitive material comprising a support having provided thereon at least one blue-sensitive silver halide emulsion layer containing a color coupler for forming a yellow color, at least one green-sensitive silver halide emulsion layer containing a color coupler for forming a magenta color, at least one red-sensitive silver halide emulsion layer containing a color coupler for forming a cyan color, and at least one hydrophilic colloid layer, and the first characteristic feature of this light-sensitive material is that the hydrophilic colloid layer contains a compound represented by Formula (I) below. ##STR5##
In this Formula (I), R.sub.1 represents a hydrogen atom, alkyl, alkenyl, aryl, a heterocyclic ring, ureido, sulfonamide, sulfamoyl, sulfonyl, sulfinyl, alkylthio, arylthio, oxycarbonyl, acyl, carbamoyl, cyano, alkoxy, aryloxy, amino, or amide, Q represents --O-- or --NR.sub.2 -wherein R.sub.2 represents a hydrogen atom, alkyl, aryl, or a heterocyclic group.
R.sub.3, R.sub.4, and R.sub.5 each represent a hydrogen atom, alkyl, or aryl, and R.sub.4 and R.sub.5 may be bonded to each other to form a 6-membered ring.
R.sub.6 represents a hydrogen atom, alkyl, aryl, or amino.
L.sub.1, L.sub.2, and L.sub.3 each represent methine, and k is an integer of 0 or 1.
When the above compound is used as a filter dye, the compound can be used in a given effective amount, but the compound is preferably used such that an optical density ranges between 0.05 and 3.0. The use amount is preferably 1 to 1,000 mg per 1 m.sup.2 of the light-sensitive material.
When the compound is used as a component other than the filter dye, the compound can also be used in a given effective amount. A practical use amount in this case is the same as the described above.
The dye represented by Formula (I) of the present invention can be dispersed in the hydrophilic colloid layer (e.g., an interlayer, a protective layer, an antihalation layer, and a filter layer) through various conventional methods. A practical example is the method described in JP-A-3-173383.
Although the dye according to the present invention can be dispersed in emulsion layers and other hydrophilic colloid layers, it is preferred to disperse the dye in a layer farther from a support than a green-sensitive silver halide emulsion layer. In a light-sensitive material having a yellow filter layer, the dye is most preferably dispersed in this yellow filter layer. This is so because the dye of the present invention has a sharper light absorption for a particular wavelength than that of yellow colloidal silver and therefore a sensitivity is raised in a green-sensitive emulsion layer more significantly when the dye is used in the yellow filter layer than when colloidal silver is used.
Practical examples of a compound represented by Formula (I) of the present invention are presented below, but the invention is not limited to these examples. ##STR6##
The above-mentioned compounds represented by Formula (I) can be synthesized by the method described in JP-A-4-348342.
The second characteristic feature of the light-sensitive material of the present invention is that, in order to improve color reproduction, at least one red-sensitive silver halide emulsion layer for forming a cyan color undergoes inhibition caused by the interlayer effect of a donor layer which is spectrally sensitized with a sensitizing dye represented by Formula (II) or (III) below. ##STR7##
In this Formula (II), R.sub.11, R.sub.12, R.sub.13, and R.sub.14 may be the same or different and each represents a hydrogen atom, a halogen atom, alkyl, aryl, alkoxy, aryloxy, aryloxycarbonyl, alkoxycarbonyl, amino, acyl, cyano, carbamoyl, sulfamoyl, carboxyl, or an acyloxy group.
R.sub.11 and R.sub.12 or R.sub.13 and R.sub.14 do not represent a hydrogen atom simultaneously.
R.sub.15 and R.sub.16 may be the same or different and each represent an alkyl group.
R.sub.17 represents an alkyl having three or more carbon atoms, aryl, or aralkyl group.
Alkyl, aryl, alkoxy, aryloxy, aryloxycarbonyl, alkoxycarbonyl, amino, acyl, carbamoyl, solfamoyl, aralkyl, or acyloxy group described above include the group having a substituent.
X.sub.1 represents a counter anion, and m is an integer of 0 or 1, and m=0 when intramolecular salt is to be formed. ##STR8##
In this Formula (III), R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, and R.sub.30 each have the same meaning as that of R.sub.11, R.sub.31 and R.sub.32 each have the same meaning as that of R.sub.15.
Y represents a sulfur atom, a selenium atom, or an oxygen atom, X.sub.2 has the same meaning as that of X.sub.1, and n has the same meaning as that of m.
Preferable examples of substituents in a compound represented by Formula (II) used in the present invention are shown below. That is, preferable examples of R.sub.11, R.sub.12, R.sub.13, and R.sub.14 are an alkyl group {e.g., methyl, ethyl, propyl, isopropyl, butyl, branched butyl (e.g., isobutyl and tert-butyl), pentyl, branched pentyl (e.g., isopentyl and tert-pentyl), vinylmethyl, and cyclohexyl} with 10 or less carbon atoms, an aryl group (e.g., phenyl, 4-methylphenyl, 4-chlorophenyl, and naphthyl) with 10 or less carbon atoms, an aralkyl group (e.g., benzyl, phenethyl, and 3-phenylpropyl) with 10 or less carbon atoms, an alkoxy group (e.g., methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, benzyloxy, and phenethyloxy) with 10 or less carbon atoms, an aryloxy (e.g., phenoxy, 4-methylphenoxy, 4-chlorophenoxy, and naphthyloxy) with 10 or less carbon atoms, a halogen atom (e.g., fluorine, chlorine, bromine, and iodine), a haloalkyl group (e.g., trifluoromethyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, and benzyloxycarbonyl) with 10 or less carbon atoms, an aryloxycarbonyl group (e.g., phenyloxycarbonyl, 4-methylphenylcarbonyl, 4-chlorophenyloxycarbonyl, and naphthyloxycarbonyl) with 10 or less carbon atoms, an acylamino group (e.g., acetylamino, propionylamino, and benzoylamino) with 8 or less carbon atoms, an acyl group (e.g., acetyl, propionyl, benzoyl, and mesyl) with 10 or less carbon atoms, cyano, a carbamoyl group (e.g., carbamoyl, N,N-dimethylcarbamoyl, and morpholinocarbamoyl) with 6 or less carbon atoms, a carboxyl group, and an acyloxy group (acetyloxy, propionyloxy, and benzoyloxy) with 10 or less carbon atoms. In a compound represented by Formula (II), it is most preferred that R.sub.11 and R.sub.13 be hydrogen atoms, R.sub.12 be chlorine or a phenyl group, and R14 be chlorine or a phenyl group.
Examples of R.sub.15 and R.sub.16 are an alkyl group (e.g., methyl, ethyl, propyl, vinylmethyl, butyl, pentyl, hexyl, heptyl, and octyl) with 8 or less carbon atoms and an aralkyl group (e.g., benzyl, phenethyl, and 3-phenylpropyl) with 10 or less carbon atoms. Examples of the substituents of R.sub.15 and R.sub.16 are hydroxyl, carboxyl, sulfo, cyano, a halogen atom (e.g., fluorine, chlorine, and bromine), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, and benzyloxycarbonyl) with 8 or less carbon atoms, an alkoxy group (e.g., methoxy, ethoxy, butyloxy, benzyloxy, and phenethyloxy) with 8 or less carbon atoms, an aryloxy group (e.g., phenoxy and p-tolyloxy) with 8 or less carbon atoms, an acyloxy group (e.g., acetyloxy, propionyloxy, and benzoyloxy) with 8 or less carbon atoms, an acyl group (e.g., acetyl, propionyl, benzoyl, and 4-fluorobenzoyl) with 8 or less carbon atoms, a carbamoyl group (e.g., carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, and methanesulfonylaminocarbonyl) with 6 or less carbon atoms, a sulfamoyl group (e.g., sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl, and acetylaminosulfonyl) with 6 or less carbon atoms, and an aryl group (e.g., phenyl, p-fluorophenyl, p-hydroxyphenyl, p-carboxyphenyl, and p-sulfophenyl) with 10 or less carbon atoms.
R.sub.15 and R.sub.16 are more preferably sulfoethyl, sulfopropyl, sulfobutyl, 1-methylsulfopropyl, carboxymethyl, and carboxyethyl, and most preferably sulfopropyl and sulfobutyl.
Preferable examples of R.sub.17 are an alkyl group (e.g., propyl, isopropyl, cyclopropyl, butyl, a branched butyl group (e.g., isobutyl and tert-butyl), pentyl, branched pentyl (e.g., isopentyl and tert-pentyl), and cyclohexyl) with 3 to 8 carbon atoms, an aryl group (e.g., phenyl and p-tolyl) with 10 or less carbon atoms, and an aralkyl group (e.g., benzyl, phenethyl, and 3-phenylpropyl) with 10 or less carbon atoms.
R.sub.17 is preferably an alkyl group (including substituted alkyl) or an aryl group (including substituted aryl) each having L, B.sub.1, B.sub.2, B.sub.3, and B.sub.4 which satisfy relations L>4.11, B.sub.1 >1.52, B.sub.2 >1.90, B.sub.3 >1.90, and B.sub.4 >2.97. These L, B.sub.1, B.sub.2, B.sub.3, and B.sub.4 represent the values (unit=.ANG.) of L, B.sub.1, B.sub.2, B.sub.3, and B.sub.4 of STERIMOL parameters described in, e.g., A. Verloop, W. Hoogenstraaten, and J. Tipker, "Drug Design, Vol. VII" (E. J. Ariens ed.), Academic Press, New York (1976), pp. 180 to 185.
Practical examples of R.sub.17 are propyl, isopropyl, cyclopropyl, butyl, isobutyl, chloromethyl, 2-chloroethyl, 3-chloropropyl, phenyl, and benzyl. R.sub.17 is most preferably propyl, phenyl, or benzyl.
In Formula (III), R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, and R.sub.30 have the same meaning as that of R.sub.11, and R.sub.31 and R.sub.32 have the same meaning as that of R.sub.15. Y represents a sulfur atom, a selenium atom, or an oxygen atom. X.sub.2 has the same meaning as that of X.sub.1, and n has the same meaning as that of m.
The above-mentioned compounds represented by Formulas (II) and (III) used in the present invention can be synthesized by the methods described in, e.g., F. M. Hamer, "Heterocyclic Compounds - Cyanine Dyes and Related Compounds," John Wiley & Sons, New York, London, 1964; D. M. Sturmer, "Heterocyclic Compounds -Special topics in heterocyclic chemistry-," Chapter 18, Paragraph 14, pages 482 to 515, John Wiley & Sons, New York, London, 1977; and "Rodd's Chemistry of Carbon Compounds," 2nd ed., Vol. IV, part B, 1977, Chapter 15, pages 369 to 422 and 2nd ed., part B, 1985, Chapter 15, pages 267 to 296, Elsvier Science Publishing Company Inc., New York.
Practical examples of compounds represented by Formulas (II) and (III) of the present invention are presented below, but the invention is not limited to these examples. ##STR9##
The use amount of the sensitizing dye represented by Formula (II) or (III) above is 20% or more of the amount of dyes used in the donor layer with the interlayer effect. The actual addition amount of the sensitizing dye is preferably 4.times.10.sup.-6 to 8.times.10.sup.-3 mol, and more preferably 1.times.10.sup.-5 to 2.times.10.sup.-3 mol per mol of a silver halide. This sensitizing dye can be added at any stage, which has been conventionally known to be useful, during preparation of an emulsion.
Although the above sensitizing dye can be used either singly or in combination with any other dye, it is more preferred to use it together with a cyanine-based dye.
In the light-sensitive material of the present invention, the donor layer with the interlayer effect, which is spectrally sensitized with the sensitizing dye represented by Formula (II) or (III) above, can be arranged at any position provided that the layer is nearer to a support than the hydrophilic layer containing a compound represented by Formula (I).
A preferable silver halide contained in photographic emulsion layers of the photographic light-sensitive material of the present invention is silver bromoiodide, silver iodochloride, or silver bromochloroiodide each containing about 30 mol % or less of silver iodide. The silver halide is most preferably silver bromoiodide or silver bromochloroiodide each containing about 2 mol % to about 10 mol % of silver iodide.
Silver halide grains contained in the photographic emulsion may have regular crystals, such as cubic, octahedral, or tetradecahedral crystals, or irregular crystals, such as spherical or tabular crystals. The silver halide grains can also have crystal defects, such as twin planes, or may take composite shapes of these shapes.
The silver halide may consist of fine grains having a grain size of about 0.2 .mu.m or less or large grains having a projected area diameter of about 10 .mu.m, and the emulsion may be either a polydisperse or monodisperse emulsion.
Silver halide photographic emulsions which can be used in the light-sensitive material of the present invention can be prepared by the methods described in, for example, "I. Emulsion preparation and types," Research Disclosure (RD) No. 17643 (December, 1978), pp. 22 and 23, RD No. 18716 (November, 1979), page 648, and RD No. 307105 (November, 1989), pp. 863 to 865; P. Glafkides, "Chemie et Phisique Photographique", Paul Montel, 1967; G. F. Duffin, "Photographic Emulsion Chemistry", Focal Press, 1966; and V. L. Zelikman et al., "Making and Coating Photographic Emulsion", Focal Press, 1964.
Monodisperse emulsions described in, for example, U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferred.
Also, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. The tabular grains can be easily prepared by methods described in, e.g., Gutoff, "Photographic Science and Engineering", Vol. 14, pp. 248 to 257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157.
A crystal structure may be uniform, may have different halogen compositions in the internal and the external layer thereof, or may be a layered structure. Alternatively, a silver halide may be bonded to another silver halide having a different composition via an epitaxial junction or to a compound except for a silver halide, such as silver rhodanide or zinc oxide. A mixture of grains having various types of crystal shapes may also be used.
The above emulsion may be any of a surface latent image type emulsion which mainly forms a latent image on the surface of a grain, an internal latent image type emulsion which forms a latent image in the interior of a grain, and an emulsion of another type which has latent images both on the surface and in the interior of a grain. However, the emulsion must be a negative type emulsion. In this case, the internal latent image type emulsion may be a core/shell internal latent image type emulsion described in JP-A-63-264740. A method of preparing this core/shell internal latent image type emulsion is described in JP-A-59-133542. Although the thickness of a shell of this emulsion depends on, e.g., development conditions, it is preferably 3 to 40 nm, and most preferably 5 to 20 nm.
A silver halide emulsion is normally subjected to physical ripening, chemical ripening, and spectral sensitization steps before being used. The kinds of additives for use in these steps are described in Research Disclosure Nos. 17643, 18716, and 307105, and the kinds of additive and the relevant part in the publications are summarized in the following table.
TABLE__________________________________________________________________________ Kinds of RD17643 RD18716 RD307105No. additives [Dec. 1978] [Nov. 1979] [Nov. 1989]__________________________________________________________________________1. Chemical page 23 page 648, right page 866 sensitizers column2. Sensitivity page 648, right intensifiers column3. Spectral sensiti- pages 23-24 From page 648, right pages 866 to 868 zers, Super column to page sensitizers 649, right column4. Brighteners page 24 page 647, right page 868 column5. Antifoggants, pages 24-25 page 649, right pages 868 to 870 Stabilizers column6. Light absorbent, pages 25-26 From page 649, right page 873 Filter dye, Ultra- column to page violet absorbents 650, left column7. Stain- page 25, page 650, left to page 872 inhibitors right column right columns8. Dye image page 25 page 650, left page 872 stabilizers column9. Hardeners page 26 page 651, left pages 874 to 875 column10. Binders " page 651, left pages 873 to 874 column Plasticizers, page 27 page 650, right page 876 Lubricants column Coating pages 26-27 page 650, right pages 875 to 876 auxiliaries, column Surfactants Anti-static agents page 27 page 650, right pages 876 to 877 column Matting agents pages 878 to 879__________________________________________________________________________
The silver halide light-sensitive material of the present invention can achieve its effect more easily when applied to a lens-incorporating film unit, such as those described in JP-B-2-32615 ("JP-B" means Published Examined Japanese Patent Application) and Published Examined Japanese Utility Model Application No. 3-39784.

EXAMPLES
The present invention will now be described in greater detail by reference to the following examples. These examples, however, are not intended to be interpreted as limiting the scope of the present invention.
Example 1
Layers having the following compositions were formed on a subbed triacetylcellulose film support to make a sample 101 as a multilayered color light-sensitive material.
Compositions of Light-Sensitive Layers
The coating amount of each of a silver halide and colloidal silver is represented by a silver amount in units of g/m.sup.2, and that of each of a coupler, an additive, and gelatin is represented in units of g/m.sup.2. The coating amount of a sensitizing dye is represented by the number of mols per mol of a silver halide in the same layer. Note that symbols representing additives have the following meanings. Note also that when an additive has a plurality of effects, a representative one of the effects is shown.
UV; ultraviolet absorbent, Solv; high-boiling organic solvent, ExF; dye, ExS; sensitizing dye, ExC; cyan coupler, ExM; magenta coupler, ExY; yellow coupler, Cpd; additive.
______________________________________1st layer (Antihalation layer)Black colloidal silver 0.15silverGelatin 2.33UV-1 3.0 .times. 10.sup.-2UV-2 6.0 .times. 10.sup.-2UV-3 7.0 .times. 10.sup.-2ExF-1 1.0 .times. 10.sup.-2ExF-2 4.0 .times. 10.sup.-2ExF-3 5.0 .times. 10.sup.-3ExM-3 0.11Cpd-5 1.0 .times. 10.sup.-3Solv-1 0.16Solv-2 0.102nd layer (Low-speed red-sensitive emulsion layer)Silver bromoiodide emulsion A 0.35silverSilver bromoiodide emulsion B 0.18silverGelatin 0.77ExS-1 2.4 .times. 10.sup.-4ExS-2 1.4 .times. 10.sup.-4ExS-5 2.3 .times. 10.sup.-4ExS-7 4.1 .times. 10.sup.-6ExC-1 9.0 .times. 10.sup.-2ExC-2 5.0 .times. 10.sup.-3ExC-3 4.0 .times. 10.sup.-2ExC-5 8.0 .times. 10.sup.-2ExC-6 2.0 .times. 10.sup.-2ExC-9 2.5 .times. 10.sup.-2Cpd-4 2.2 .times. 10.sup.- 23rd layer (Medium-speed red-sensitive emulsionlayer)Silver bromoiodide emulsion C 0.55silverGelatin 1.46ExS-1 2.4 .times. 10.sup.-4ExS-2 1.4 .times. 10.sup.-4ExS-5 2.4 .times. 10.sup.-4ExS-7 4.3 .times. 10.sup.-6ExC-1 0.19ExC-2 1.0 .times. 10.sup.-2ExC-3 1.0 .times. 10.sup.-2ExC-4 1.6 .times. 10.sup.-2ExC-5 0.19ExC-6 2.0 .times. 10.sup.-2ExC-7 2.5 .times. 10.sup.-2ExC-9 3.0 .times. 10.sup.-2Cpd-4 1.5 .times. 10.sup.-24th layer (High-speed red-sensitive emulsion layer)Silver bromoiodide emulsion D 1.05silverGelatin 1.38ExS-1 2.0 .times. 10.sup.-4ExS-2 1.1 .times. 10.sup.-4ExS-5 1.9 .times. 10.sup.-4ExS-7 1.4 .times. 10.sup.-5ExC-1 2.0 .times. 10.sup.-2ExC-3 2.0 .times. 10.sup.-2ExC-4 9.0 .times. 10.sup.-2ExC-5 5.0 .times. 10.sup.-2ExC-8 1.0 .times. 10.sup.-2ExC-9 1.0 .times. 10.sup.-2Cpd-4 1.0 .times. 10.sup.-3Solv-1 0.70Solv-2 0.155th layer (Interlayer)Gelatin 0.62Cpd-1 0.13Polyethylacrylate latex 8.0 .times. 10.sup.-2Solv-1 8.0 .times. 10.sup.-26th layer (Low-speed green-sensitive emulsion layer)Silver bromoiodide emulsion E 0.10silverSilver bromoiodide emulsion F 0.28silverGelatin 0.31ExS-3 1.0 .times. 10.sup.-4ExS-4 3.1 .times. 10.sup.-4ExS-5 6.4 .times. 10.sup.-5ExM-1 0.12ExM-7 2.1 .times. 10.sup.-2Solv-1 0.09Solv-3 7.0 .times. 10.sup.-37th layer (Medium-speed green-sensitive emulsionlayer)Silver bromoiodide emulsion G 0.37silverGelatin 0.54ExS-3 2.7 .times. 10.sup.-4ExS-4 8.2 .times. 10.sup.-4ExS-5 1.7 .times. 10.sup.-4ExM-1 0.27ExM-7 7.2 .times. 10.sup.-2ExY-1 5.4 .times. 10.sup.-2Solv-1 0.23Solv-3 1.8 .times. 10.sup.-28th layer (High-speed green-sensitive emulsion layer)Silver bromoiodide emulsion H 0.53silverGelatin 0.61ExS-4 4.3 .times. 10.sup.-4ExS-5 8.6 .times. 10.sup.-5ExS-8 2.8 .times. 10.sup.-5ExM-2 5.5 .times. 10.sup.-3ExM-3 1.0 .times. 10.sup.-2ExM-5 1.0 .times. 10.sup.-2ExM-6 3.0 .times. 10.sup.-2ExY-1 1.0 .times. 10.sup.-2ExC-1 4.0 .times. 10.sup.-3ExC-4 2.5 .times. 10.sup.-3Cpd-6 1.0 .times. 10.sup.-2Solv-1 0.129th layer (Interlayer)Gelatin 0.56UV-4 4.0 .times. 10.sup.-2UV-5 3.0 .times. 10.sup.-2Cpd-1 4.0 .times. 10.sup.-2Polyethylacrylate latex 5.0 .times. 10.sup.-2Solv-1 3.0 .times. 10.sup.-210th layer (Donor layer having interlayer effect onred-sensitive layer)Silver bromoiodide emulsion I 0.40silverSilver bromoiodide emulsion J 0.20silverSilver bromoiodide emulsion K 0.39silverGelatin 0.87ExS-3 6.7 .times. 10.sup.-4ExM-2 0.16ExM-4 3.0 .times. 10.sup.-2ExM-5 5.0 .times. 10.sup.-2ExY-2 2.5 .times. 10.sup.-3ExY-5 2.0 .times. 10.sup.-2Solv-1 0.30Solv-5 3.0 .times. 10.sup.-211th layer (Yellow filter layer)Yellow colloidal silver 9.0 .times. 10.sup.-2silverGelatin 0.84Cpd-1 5.0 .times. 10.sup.-2Cpd-2 5.0 .times. 10.sup.-2Cpd-5 2.0 .times. 10.sup.-3Solv-1 0.13H-1 0.2512th layer (Low-speed blue-sensitive emulsion layer)Silver bromoiodide emulsion L 0.50silverSilver bromoiodide emulsion M 0.40silverGelatin 1.75ExS-6 9.0 .times. 10.sup.-4ExY-1 8.5 .times. 10.sup.-2ExY-2 5.5 .times. 10.sup.-3ExY-3 6.0 .times. 10.sup.-2ExY-5 1.00ExC-1 5.0 .times. 10.sup.-2ExC-2 8.0 .times. 10.sup.-2Solv-1 0.5413th layer (Interlayer)Gelatin 0.30ExY-4 0.14Solv-1 0.1414th layer (High-speed blue-sensitive emulsion layer)Silver bromoiodide emulsion N 0.40silverGelatin 0.95ExS-6 2.6 .times. 10.sup.-4ExY-2 1.0 .times. 10.sup.-2ExY-3 2.0 .times. 10.sup.-2ExY-5 0.18ExC-1 1.0 .times. 10.sup.-2Solv-1 9.0 .times. 10.sup.-215th layer (1st protective layer)Fine grain silver bromoiodide emulsion O 0.12silverGelatin 0.63UV-4 0.11UV-5 0.18Cpd-3 0.10Solv-4 2.0 .times. 10.sup.-2Polyethylacrylate latex 9.0 .times. 10.sup.-216th layer (2nd protective layer)Fine grain silver bromoiodide emulsion O 0.36silverGelatin 0.85B-1 (diameter 2.0 .mu.m) 8.0 .times. 10.sup.-2B-2 (diameter 2.0 .mu.m) 8.0 .times. 10.sup.-2B-3 2.0 .times. 10.sup.-2W-5 2.0 .times. 10.sup.-2H-1 0.18______________________________________
In addition to the above components, the sample thus manufactured was added with 1,2-benzisothiazolin-3-one (200 ppm on average with respect to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm on average with respect to gelatin), and 2-phenoxyethanol (about 10,000 ppm on average with respect to gelatin). In order to improve shelf stability, processability, a resistance to pressure, antiseptic and mildewproofing properties, antistatic properties, and coating properties, the individual layers were further added with W-1 to W-6, B-1 to B-6, F-1 to F-16, iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.
The emulsions represented by the abbreviations described above are shown in Table 1 below.
TABLE 1__________________________________________________________________________ Average grain size Variation represented coefficient Average by (%) of Silver amount ratio Grain AgI equivalent- grain size Diameter/ [core/intermediate/ structure content sphere distribu- thickness shell] (AgI and grain (mole %) diameter (.mu.m) tion ratio content) shape__________________________________________________________________________Emulsion A 4.7 0.40 10 1.0 [4/1/5] [1/38/1] Triple structure cubic grain B 6.0 0.49 23 2.0 [1/2] (16/1) Double structure plate grain C 8.4 0.65 23 2.2 [3/5/2] (0/14/7) Triple structure plate grain D 8.8 0.65 15 3.5 [12/59/29] (0/12/6) Triple structure plate grainE 4.0 0.35 25 2.8 -- Uniform structure plate grainF 4.0 0.50 18 4.0 -- Uniform structure tabular grainEmulsion G 3.5 0.55 15 3.5 [12/59/29] (0/5/2) Triple structure tabular grain H 10.0 0.70 20 5.5 [12/59/29] (0/13/8) Triple structure tabular grain I 3.8 0.70 15 3.5 [12/59/29] (0/5/3) Triple structure tabular grain J 8.0 0.65 28 2.5 [1/2] (18/3) Double structure plate grain K 10.3 0.40 15 1.0 [1/3] (29/4) Double structure octahedral grainEmulsion L 9.0 0.66 19 5.8 [8/59/33] (0/11/8) Triple structure tabular grainM 2.5 0.46 30 7.0 -- Uniform structure tabular grainN 13.9 1.30 25 3.0 [7/13] (34/3) Double structure plate grainO 2.0 0.07 15 1.0 -- Uniform structure fine grain__________________________________________________________________________
In Table 1,
(1) The emulsions A to N were subjected to reduction sensitization during grain preparation by using thiourea dioxide and thiosulfonic acid in accordance with the examples in JP-A-2-191938.
(2) The emulsions A to N were subjected to gold sensitization, sulfur sensitization, and selenium sensitization in the presence of the spectral sensitizing dyes described in the individual light-sensitive layers and sodium thiocyanate in accordance with the examples in JP-A-3-237450.
(3) The preparation of tabular grains was performed by using low-molecular weight gelatin in accordance with the examples in JP-A-1-158426.
(4) Dislocation lines as described in JP-A-3-237450 were observed in tabular grains and regular crystal grains having a grain structure when a high-voltage electron microscope was used.
(5) The emulsions A to N contained iridium in the interior of their grains through the use of the method described in B. H. Carroll, Photographic Science and Engineering, 24, 265 (1980).
The compounds used in the formation of the individual layers were as follows. ##STR10##
Samples 102 to 111 were made following the same procedures as for the sample 101 exception that the sensitizing dye and the coupler amount in the 10th layer and the yellow colloidal silver in the 11th layer of the sample 101 were changed as shown in Table 2 below. A list of the samples 101 to 102 is given in Table 2.
TABLE 2__________________________________________________________________________Sensitizing dye in Coupler amount10th layer in 10th layer* Compound in 11th layer__________________________________________________________________________Sample 101 ExS-3 6.7 .times. 10.sup.-4 100 Yellow colloidal silver 102 ExS-3 6.7 .times. 10.sup.-4 98 D-101 103 ExS-3 6.7 .times. 10.sup.-4 98 D-201 104 I-1 6.9 .times. 10.sup.-4 95 Yellow colloidal silver 105 I-1 6.9 .times. 10.sup.-4 91 D-101 106 I-7 6.6 .times. 10.sup.-4 96 Yellow colloidal silver 107 I-7 6.6 .times. 10.sup.-4 89 D-101 108 II-1 7.3 .times. 10.sup.-4 96 Yellow colloidal silver 109 II-1 7.3 .times. 10.sup.-4 88 D-101 110 II-3 7.4 .times. 10.sup.-4 96 Yellow colloidal silver 111 II-3 7.4 .times. 10.sup.-4 90 D-201__________________________________________________________________________ *The coupler amount in the 10th layer is represented by a relative value assuming that the coupler amount in the sample 101 is 100.
When the dye of the present invention was to be used in place of the yellow colloidal silver in the 11th layer, a material prepared by dissolving the dye in a solvent mixture of ethyl acetate and tricresylphosphate and dispersing the resultant material in an aqueous gelatin solution by using a colloid mill was used. The addition amount was 3.2.times.10.sup.-4 mol/m.sup.2 in all the examples. The coupler amount in the 10th layer was controlled such that a color formation quantity equivalent to that of the 10th layer of the sample 101 was obtained under white exposure.
These samples were subjected to the following color developing process.
______________________________________Process Time Temperature______________________________________Color development 3 min. 15 sec. 38.degree. C.Bleaching 6 min. 30 sec. 38.degree. C.Washing 2 min. 10 sec. 24.degree. C.Fixing 4 min. 20 sec. 38.degree. C.Washing 3 min. 15 sec. 24.degree. C.Stabilization 1 min. 05 sec. 38.degree. C.______________________________________
The compositions of the processing solutions used in the individual steps were as follows.
______________________________________Color developing solutionDiethylenetriaminepentaacetic acid 1.0 g1-hydroxyethylidene-1,1- 2.0 gdiphosphonic acidSodium sulfite 4.0 gPotassium carbonate 30.0 gPotassium bromide 1.4 gPotassium iodide 1.3 mgHydroxylamine sulfate 2.4 g4-(N-ethyl-N-.beta.-hydroxylethylamino)- 4.5 g2-methylaniline sulfateWater to make 1.0 lpH 10.0Bleaching solutionFerric ammonium ethylenediamine- 100.0 gtetraacetateDisodium ethylenediaminetetraacetate 10.0 gAmmonium bromide 150.0 gAmmonium nitrate 10.0 gWater to make 1.0 lpH 6.0Fixing solutionDisodium ethylenediaminetetraacetate 1.0 gSodium sulfite 4.0 gAqueous ammonium thiosulfate 175.0 mlsolution (70%)Sodium bisulfite 4.6 gWater to make 1.0 lpH 6.6Stabilizing solutionFormalin (40%) 2.0 mlPolyoxyethylene-p-monononylphenylether 0.3 g(average polymerization degree 10)Water to make 1.0 l______________________________________
When the samples 101 to 111 were wedge-exposed to white light and subjected to the processing (to be described later), samples with substantially equal sensitivities and gradations could be obtained.
The granularity of the magenta dye image of each resultant sample was measured by a conventional RMS (Root Mean Square) method. The determination of granularity according to the RMS method is known to those skilled in the art and described as an article titled "RMS Granularity; Determination of Just noticeable difference" in "Photographic Science and Engineering," Vol. 19, No. 4 (1975), pp. 235 to 238. An aperture of 48 fm was used in the measurement.
In addition, a dominant wavelength in reproduction of each of the samples 101 to 111 was obtained by the method described in JP-A-62-160448 for the purpose of evaluating the reproduction of wavelengths of a spectrum. That is, a difference (.lambda.-.lambda..sub.0) between a wavelength .lambda..sub.0 of testing light and a dominant wavelength .lambda. of a reproduced color was obtained at 450 to 600 nm, and the obtained values were averaged as follows: ##EQU1## The results are summarized in Table 3 below. The testing light was spectral light with an excitation purity of 0.7+white light. The exposure amount was 0.04 lux.sec and 0.01 lux.sec for the white light mixed. The latter value is supposed to better represent the characteristics of color reproduction in underexposure.
The obtained results are summarized in Table 3 below.
TABLE 3__________________________________________________________________________R, M, S of magentaD = fog + 0.3 D = fog + 0.8 .DELTA..lambda.Sample No. (.times.10.sup.-4) (.times.10.sup.-4) 0.04 Lux .multidot. sec 0.01 Lux .multidot. sec__________________________________________________________________________101 12 11 2.2 4.1 Comparative example102 11 11 2.1 4.0 Comparative example103 9 10 2.3 4.0 Comparative example104 11 10 2.2 4.2 Comparative example105 7 5 1.8 3.7 Present invention106 9 9 2.0 3.9 Comparative example107 5 5 1.7 3.3 Present invention108 10 8 1.9 3.8 Comparative example109 4 4 1.6 2.9 Present invention110 9 8 2.0 3.9 Comparative example111 6 4 1.7 3.2 Present invention__________________________________________________________________________
As is obvious from the results as shown in Table 3, each sample of the present invention could be improved significantly in granularity as compared with the comparative samples.
It was also found that the samples of the present invention were also very effective in color reproduction.
Example 2
Each of the samples 101 to 111 of Example 1 was processed into the form of an "UTSURUNDESU FLASH (tradename)" (Quick Snap) available from Fuji Photo Film Co., Ltd., and photography was performed by using each lens-incorporating film thus manufactured. When the results of photography were evaluated, it was found that each sample of the present invention exhibited a high print quality, indicating the obvious improving effect of the present invention.

Number	Name	Date
3933510	Shiba et al.	Jan 1976
4904578	Tanaka	Feb 1990
5053324	Sasaki	Oct 1991
5198332	Ikagawa et al.	Mar 1993
5213957	Adachi	May 1993
5296344	Jimbo et al.	Mar 1994

Silver halide color photographic light-sensitive material

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