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(11) | EP 0 422 595 A1 |
| (12) | EUROPEAN PATENT APPLICATION |
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| (54) | A silver halide color photographic light-sensitive material |
| (57) There is disclosed a silver halide light-sensitive photographic material having
improved graininess and processing stability. The light-sensitive material has on
a support at least one green-sensitive layer containing a magenta coupler represented
by Formula M-I and a compound represented by Formula A-I:
wherein Z represents the group of non-metallic atoms for forming a nitrogen containing heterocyclic ring; X represents a hydrogen atom or a substituent capable of splitting off by a reaction with an oxidation product of a developer; and R represents a hydrogen atom or a substituent; Formula A-I H O (̵J)̵ C O O Y wherein J represents a divalent organic group; Y represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkenyl group and a heterocycilc group. |
FIELD OF THE INVENTION
[0001] The present invention relates to a silver halide color photographic light-sensitive material having an excellent processing stability and improved graininess.
BACKGROUND OF THE INVENTION
[0002] In recent years, there have been studying light-sensitive materials having higher image quality, in particular, more excellent color reproducibility, graininess and sharpness.
[0003] U.S. Patent No. 3,725,067, Japanese Patent Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 42045/1983, 171956/1984, 43659/1985 and 190779/1985 each disclose the methods of improving color reproducibility by use of magenta couplers which form dyes having no secondary absorptions.
[0004] The pyrazoloazole magenta couplers significantly improve the reproducibility of red color while there exists such a problem that a density of a dye image is liable to vary by change of processing conditions, in particular, pH change of a developer.
[0005] In the invention, it has been found that the preceding problem can be solved by use of the pyrazoloazole magenta couplers in combination with a compound having a hydroxyl group and an ester group.
SUMMARY OF THE INVENTION
[0006] The primary object of the invention is to provide a silver halide color photographic light-sensitive material having an improved processing stability and graininess.
[0007] The secondary object of the invention is to provide a light-sensitive material capable of providing a dye image having a stable color density against change of processing conditions, in particular, pH change of a developer.
[0008] The above objects can be attained by a silver halide color photographic light-sensitive material comprising a support and provided thereon plural light-sensitive layers including at least one green-sensitive layer, wherein the at least one green-sensitive layer contains a magenta coupler represented by Formula M-I and a compound represented by Formula A-I:
wherein Z represents a group of non-metal atoms necessary to form a nitrogen-containing heterocycle which may have a substituent; X represents a hydrogen atom or a group which can be released by a reaction with an oxidation product of a color developing agent; and R represents a hydrogen atom or a substituent;
Formura A-I
H O (̵J)̵ C O O Y
wherein J represents a divalent organic group; and Y represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkenyl group and a heterocyclic group.
DETAILED DESCRIPTION OF THE INVENTION
[0009] In Formula M-1, the examples of the substituent represented by R are an alkyl group, an aryl group, an anilino group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkenyl group, a cycloalkyl group, a halogen atom, a cycloalkenyl group, an alkynyl group, a heterocyclic group, a sulfonyl group, a sulfinyl group, a phosphonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkylamino group, an imido group, an ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclicthio group, a spiro compound residue and a bridged hydrocarbon residue.
[0010] The respective groups represented by R are as follows: the alkyl group has preferably 1 to 32 carbon atoms and may be linear or branched; the aryl group is preferably phenyl; the examples of the acylamino group are alkylcarbonylamino and arylcarbonylamino; the examples of the sulfonamide group are alkylsufonylamino and arylsulfonylamino; the alkyl and aryl components in the alkylthio and arylthio groups may be the same as the above alkyl and aryl groups; the alkenyl group has preferably 2 to 32 carbon atoms and may be linear or branched; the cycloalkyl and cycloalkenyl groups each have preferably 3 to 12, more preferably 5 to 7 carbon atoms; the examples of the sulfonyl group are alkylsulfonyl and arylsulfonyl; the examples of the sulfinyl group are alkylsulfinyl and arylsulfinyl; the examples of the phosphonyl group are alkylphosphonyl, alkoxyphosphonyl, aryloxyphosphonyl and arylphosphonyl; the examples of the acyl group are alkylcarbonyl and arylcarbonyl; the examples of the carbamoyl group are alkylcarbamoyl and arylcarbamoyl; the examples of the sulfamoyl group are alkylsulfamoyl and arylsulfamoyl; the examples of the acyloxy group are alkylcarbonyloxy and arylcarbonyloxy; the examples of the carbamoyloxy are alkylcarbamoyloxy and arylcarbamoyloxy; the examples of the ureido group are alkylureido and arylureido; the examples of the sulfamoylamino group are alkylsulfamoylamino and arylsufamoylamino; the heterocyclic group is preferably a 5 to 7-membered ring such as 2-furyl, 2-thienyl, 2-pyrimidyl and 2-benzothiazolyl; the heterocyclicoxy group is preferably a 5 to 7-membered ring such as 3,4,5,6-tetrahydropyranyl-2-oxy and 1-phenyltetrazole-5-oxy; the heterocyclicthio group is preferably a 5 to 7-membered ring such as 2-pyridylthio, 2-benzothiazolylthio and 2,4-diphenoxy-1,3,5-triazole-6-thio; the examples of the siloxy group are trimethylsiloxy, triethylsiloxy and dimethylbutylsiloxy; the examples of the imido group are succinic imido, 3-heptadecyl succinic imido, phthalimido and glutarimido; the spiro compound residue includes a spiro [3.3] heptane-1-yl; the examples of the bridged hydrocarbon compound residue are bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ³,⁷] decane-1-yl and 7,7-dimethyl-bicyclo [2.2.1] heptane-1-yl.
[0011] The examples of the group represented by X are a halogen atom, an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, an alkoxyoxalyoxy group, an alkylthio group, an arylthio group, a heterocyclicthio group, an alkoxythiocarbonylthio group, an acylamino group, a sulfonamide group, a nitrogen-containing heterocycle having a bonding site at the nitrogen atom, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a carboxyl group,
wherein R₁′ and Z′ are the same groups as those defined for R and Z in Formula M-I, respectively, and R₂′ and R₃′ each represent a hydrogen atom, an aryl group, an alkyl group and a heterocyclic group. Of them, a halogen atom, in particular chlorine is preferable.
[0012] The nitrogen-containing heterocycles formed by Z and Z′ are a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring, and may have the same substituents as those defined for R.
[0013] The magenta coupler represented by M-I are represented by the following Formulae M-II to M-VII:
wherein R₁ to R₈ and X represent the same groups as those defined for R and X in Formula M-I, respectively.
[0014] The magenta coupler represented by Formula M-I is represented preferably by the following Formula M-VIII:
wherein R₁, X and Z₁ represent the same groups as those defined for R, X and Z in Formula M-I, respectively.
[0015] Of the magenta couplers represented by Formulae M-II to M-VII, preferable are those represented by Formula M-II.
[0016] The substituents for the rings formed by Z in Formula M-I and Z₁ in Formula M-VIII and the groups represented by R₂ to R₆ in Formula M-II to M-VI are represented preferably by the following Formula M-IX:
Formura M-IX
- R¹ - SO₂ - R₂
wherein R₁ represents an alkylene group and R₂ represents an alkyl group, a cycloalkyl group or an aryl group. R₁ or R₂ has preferably at least one acid group. This acid group is preferably a carboxylic group or a sulfonic group, more preferably a carboxylic group or a salt thereof.
[0017] The alkylene group represented by R₁ is a linear or branched alkylene group which has preferably 2 or more, more preferably 3 to 6 carbon atoms in its linear structure. The cycloalkyl group represented by R₂ is preferably 5 to 6-membered.
[0018] When the light-sensitive material is used for forming a positive image, R and R₁ are preferably the groups represented by Formula M-X:
wherein R₉, R₁₀ and R₁₁ each represent the same groups as those defined for R, provided that two of R₉, R₁₀ and R₁₁ may combine to form a saturated or unsaturated ring such as cycloalkane, cycloalkene and heterocycle and that R₉ or R₁₁ may combine with this ring to form a bridged hydrocarbon residue.
[0019] Of the substituents represented by Formula M-X, preferable is (i) the one in which at least two of R₉ to R₁₁ are alkyl groups, or (ii) the one in which at least one of R₉ to R₁₁ is a hydrogen atom and the remaining two combine to form a cycloalkyl group.
[0020] In the case of (i), further preferable is the one in which two of R₉ to R₁₁ are alkyl groups and the remaining one is either a hydrogen atom or an alkyl group.
[0021] When the light-sensitive material is used for forming a negative image, R and R₁ are preferably those represented by Formula M-XI:
Formura M-XI
R₁₂ - CH₂ -
wherein R₁₂ is the same group as that defined for R.
[0024] The other examples of the magenta couplers usable in the invention are described in Japanese Patent Application No. 9791/1986.
[0025] The preceding magenta couplers can be synthesized by the methods described in Journal of the Chemical Society, Perkin I (1977), pp. 2047 to 2052, U.S. Patent No. 3,725,067, Japanese Patent O.P.I. Publication No. 99437/1984, 42045/1983, 162548/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985 and 190779/1985.
[0026] The preceding magenta couplers are added normally in an amount of 1 x 10⁻³ to 1 mol, preferably 1 x 10⁻² to 8 x 10⁻¹ mol per mol of silver halide, and may be used in combination with other couplers.
[0028] The examples of the divalent organic group represented by J are an alkylene group, an alkenylene group, a cycloalkylene group, a carbonyl group, a carbonyloxy group, an allylene group and a heterocyclic group, each of which may have a substituent. Of them, the above group is preferably an arylene group, more preferably a phenylene group.
[0029] The alkyl, cycloalkyl, aryl, alkenyl, alkynyl and cycloalkenyl groups represented by Y each have preferably 1 to 32 carbon atoms and may have a substituent. The alkyl, alkenyl and alkynyl groups may be either linear or branched.
[0030] The heterocyclic group represented by Y is preferably a nitrogen-containing heterocyclic group such as pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrrolinyl, imidazolidinyl, imidazolinyl, piperadinyl and piperidinyl, each of which may have a substituent.
[0032] In the invention, the magenta coupler represented by Formula M-I (hereinafter referred to as Magenta coupler M-I) and the compound represented by Formula A-I (hereinafter referred to as Compound A-I) are incorporated into at least one of the green-sensitive layers.
[0033] Magenta coupler M-I and Compound A-I can be added by a known method; Magenta coupler M-I and Compound A-I are dissolved singly or in combination in a mixed solvent of a high boiling solvent such as dibutyl phthalate and tricresyl phosphate and a low boiling solvent such as butyl acetate and propionic acid; the solution is dispersed in a gelatin solution containing a surfactant with a high-speed rotary mixer, a colloid mill or an ultrasonic apparatus; and the dispersion is added to an emulsion, or the gelatinized dispersion is cut into pieces, rinsed and then added to an emulsion.
[0034] In the invention, Magenta coupler M-I and Compound A-I are added to a silver halide emulsion after dispersing them separately by the above dispersion method, and the dispersion containing both compounds is added to an emulsion.
[0035] The amount of Compound A-I is preferably 0.01 to 10 g, more preferably 0.1 to 3.0 g per gram of Magenta coupler M-I. Compound A-I may be employed either alone or in combination.
[0037] The silver halide emulsions can be chemically sensitized by conventional methods, and can be spectrally sensitized to a prescribed wavelength region with a sensitizing dye,
[0038] The silver halide emulsion may contain such an additive as antifoggant and a stabilizer. Gelatin is preferably used as a binder.
[0039] The emulsion layers and other hydrophilic colloidal layers may be hardened and contain a plasticizer an a latex.
[0040] Also usable are a colored coupler, a competitive coupler and a compound which releases by a coupling reaction with an oxidation product of a development agent such photographically significant fragments as a development accelerator, a bleaching accelerator, a developing agent, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
[0041] There may be provided auxiliary layers such as a filter layer, an anti-hallation layer and an anti-irradiation layer. These layers and/or the emulsion layers may contain a dye which can be removed from the light-sensitive material or bleached during development.
[0042] The light-sensitive material may contain a formalin scavenger, a fluorescent bleaching agent, a matting agent, a lubricant, an image stabilizer, a surfactant, an anti-fogging agent, a development accelerator, a development retarder and a bleaching accelerator.
[0043] The examples of the support are polyethylene-laminated paper, a polyethylene terephthalate film, baryta paper and a cellulose triacetate film.
[0044] A dye image can be obtained by processing an exposed light-sensitive material by conventional methods.
EXAMPLES
[0045] The present invention will be described in more detail with reference to the following Examples.
[0046] In the examples, the amounts of ingredients are given by g/m² unless otherwise indicated. The amounts of silver halide and colloidal silver are converted to the amounts of silver,
Example 1
[0047] A multilayer color photographic light-sensitive material (Sample No. 1) was prepared by providing on a cellulose triacetate film support the layers of the following constitutions in sequence from the support.
| 1st Layer: Anti-halation layer (HC-1) | |
| Black colloidal silver | 0.20 |
| UV absorber (UV-1) | 0.20 |
| Colored coupler (CC-1) | 0.05 |
| Colored coupler (CM-1) | 0.05 |
| High boiling solvent (Oiℓ-1) | 0.20 |
| Gelatin | 1.5 |
| 2nd Layer: Intermediate layer (IL-1) | |
| UV absorber (UV-1) | 0.01 |
| High boiling solvent (Oiℓ-1) | 0.01 |
| Gelatin | 1.5 |
| 3rd Layer: Low-speed red-sensitive emulsion layer (RL) | |
| Silver iodobromide emulsion (Em-1) | 0.8 |
| Silver iodobromide emulsion (Em-2) | 0.8 |
| Sensitizing dye (SD-1) 2.5 x 10⁻⁴ (mol per mol silver) | |
| Sensitizing dye (SD-2) 2.5 x 10⁻⁴ (mol per mol silver) | |
| Sensitizing dye (SD-3) 0.5 x 10⁻⁴ (mol per mol silver) | |
| Cyan coupler (C-1) | 1.0 |
| Colored cyan coupler (CC-1) | 0.05 |
| DIR compound (D-1) | 0.002 |
| High boiling solvent (Oiℓ-1) | 0.5 |
| Gelatin | 1.5 |
| 4th Layer: high-speed red-sensitive emulsion layer(RH) | |
| Silver iodobromide emulsion (Em-3) | 2.0 |
| Sensitizing dye (SD-1) 2.0 x 10⁻⁴ (mol per mol silver) | |
| Sensitizing dye (SD-2) 2.0 x 10⁻⁴ (mol per mol silver) | |
| Sensitizing dye (SD-3) 0.1 x 10⁻⁴ (mol per mol silver) | |
| Cyan coupler (C-1) | 0.25 |
| Cyan coupler (C-2) | 0.05 |
| Colored cyan coupler (CC-1) | 0.015 |
| DIR compound (D-1) | 0.05 |
| High boiling solvent (Oiℓ-1) | 0.2 |
| Gelatin | 1.5 |
| 5th Layer: Intermediate layer (IL-2) | |
| Gelatin | 0.5 |
| 6th Layer: low-speed green-sensitive emulsion layer (GL) | |
| Silver iodobromide emulsion (Em-1) | 1.0 |
| Sensitizing dye (SD-4) 5 x 10⁻⁴ (mol per mol silver) | |
| Sensitizing dye (SD-5) 1 x 10⁻⁴ (mol per mol silver) | |
| Magenta coupler (M-A) | 0.1 |
| Magenta coupler (M-B) | 0.2 |
| Colored magenta coupler (CM-1) | 0.01 |
| DIR compound (D-3) | 0.02 |
| DIR compound (D-4) | 0.02 |
| High boiling solvent (Oiℓ-2) | 0.3 |
| Gelatin | 1.0 |
| 7th Layer: high-speed green-sensitive emulsion layer (GH) | |
| Silver iodobromide emulsion (Em-3) | 1.3 |
| Sensitizing dye (SD-6) 1.5 x 10⁻⁴ (mol per mol silver) | |
| Sensitizing dye (SD-7) 2.5 x 10⁻⁴ (mol per mol silver) | |
| Sensitizing dye (SD-8) 0.5 x 10⁻⁴ (mol per mol silver) | |
| Magenta coupler (M-A) | 0.05 |
| Magenta coupler (M-B) | 0.15 |
| Colored magenta coupler (CM-2) | 0.05 |
| DIR compound (D-3) | 0.01 |
| High boiling solvent (Oiℓ-2) | 0.5 |
| Gelatin | 1.0 |
| 8th Layer: Yellow filter layer (YC) | |
| Yellow colloid silver | 0.1 |
| Anti-stain agent (SC-1) | 0.1 |
| High boiling solvent (Oiℓ-3) | 0.1 |
| Gelatin | 0.8 |
| 9th Layer: low-speed blue-sensitive emulsion layer (BL) | |
| Silver iodobromide emulsion (Em-1) | 0.25 |
| Silver iodobromide emulsion (Em-2) | 0.25 |
| Sensitizing dye (SD-10) 7 x 10⁻⁴ (mol per mol silver) | |
| Yellow coupler (Y-1) | 0.5 |
| Yellow coupler (Y-2) | 0.1 |
| DIR compound (D-2) | 0.01 |
| High boiling solvent (Oiℓ-2) | 0.3 |
| Gelatin | 1.0 |
| 10th Layer: high-speed blue-sensitive emulsion layer (BH) | |
| Silver iodobromide emulsion (Em-4) | 0.4 |
| Silver iodobromide emulsion (Em-1) | 0.4 |
| Sensitizing dye (SD-9) 1 x 10⁻⁴ (mol per mol silver) | |
| Sensitizing dye (SD-10) 3 x 10⁻⁴ (mol per mol silver) | |
| Yellow coupler (Y-1) | 0.30 |
| Yellow coupler (Y-2) | 0.05 |
| High boiling solvent (Oiℓ-2) | 0.15 |
| Gelatin | 1.1 |
| 11th Layer: 1st protective layer (PRO-1) | |
| Fine-grained silver iodobromide emulsion (average gain size: 0.08 µm, AgI content: 2 mol%) | 0.4 |
| UV absorber (UV-1) | 0.10 |
| UV absorber (UV-2) | 0.05 |
| High boiling solvent (Oiℓ-1) | 0.1 |
| High boiling solvent (Oiℓ-3) | 0.1 |
| Formalin scavenger (HS-1) | 0.5 |
| Formalin scavenger (HS-2) | 0.2 |
| Gelatin | 1.0 |
| 12th Layer: 2nd protective layer (PRO-2) | |
| Surfactant (Su-1) | 0.005 |
| Alkaline-soluble matting agent (average grain size: 2 µm) | 0.05 |
| Polymethylmethacrylate (average grain size: 3 µm) | 0.05 |
| Lubricant (WAX-1) | 0.04 |
| Gelatin | 0.6 |
[0048] Besides the above ingredients, a coating aid (Su-2), a dispersion aid (Su-3), hardeners (H-1 and H-2), a stabilizer (ST-1), antifoggants (AF-1, AF-2) were added to each layer.
Em-1: a monodispersed core/shell type silver halide emulsion having a grain size distribution of 14% and a low silver iodide content (2 mol%) in the outermost shell (average grain size: 0.46 µm, average silver iodide content: 7.0 mol%)
Em-2: a monodispersed core/shell type silver halide emulsion having a grain size distribution of 14% and containing silver bromide in the outermost shell (average grain size: 0.30 µm, average silver iodide content: 2.0 mol%)
Em-3: a monodispersed core/shell type silver halide emulsion having a grain size distribution of 14% and alow silver iodide content (1.0 mol%) in the outermost shell (average grain size: 0.81 µm, average silver iodide content: 7.0 mol%)
Em-4: a monodispersed core/shell type silver halide emulsion having a grain size distribution of 14% and alow silver iodide content (0.5 mol%) in the outermost shell (average grain size:0.95 µm, average silver iodide content: 8.0 mol%)
[0050] Samples No. 2 to 14 were prepared in the same manner as in Sample No.1, except that the magenta couplers in the 6th and 7th layers were replaced as shown in Table 1 and that Compounds A-I were added to the 6th and 7th layers.
Table 1
| Sample No. | 6th layer | 7th layer | ||||||
| Coupler | Compound [A-I] | Coupler | Compound [A-I] | |||||
| No. | Amount | No. | Amount | No. | Amount | No. | Amount | |
| 1 (Comparison) | M-A | 0.1 | - | - | M-A | 0.18 | - | - |
| M-B | 0.2 | |||||||
| 2 (Comparison) | M-4 | 0.2 | - | - | M-4 | 0.12 | - | - |
| 3 (Comparison) | M-57 | 0.2 | - | - | M-57 | 0.1 | - | - |
| 4 (Invention) | M-4 | 0.2 | A-16 | 0.1 | M-A | 0.18 | - | - |
| 5 (Invention) | M-4 | 0.2 | A-16 | 0.1 | M-4 | 0.12 | A-16 | 0.05 |
| 6 (Invention) | M-4 | 0.2 | A-17 | 0.1 | M-4 | 0.12 | A-17 | 0.05 |
| 7 (Invention) | M-4 | 0.2 | A-2 | 0.1 | M-4 | 0.12 | A-2 | 0.05 |
| 8 (Invention) | M-4 | 0.22 | A-24 | 0.15 | M-4 | 0.12 | A-13 | 0.05 |
| 9 (Invention) | M-1 | 0.2 | A-12 | 0.1 | M-1 | 0.12 | A-12 | 0.05 |
| 10 (Invention) | M-5 | 0.2 | A-19 | 0.12 | M-5 | 0.12 | A-19 | 0.06 |
| 11 (Invention) | M-10 | 0.2 | A-18 | 0.1 | M-10 | 0.12 | A-18 | 0.05 |
| 12 (Invention) | M-57 | 0.2 | A-16 | 0.1 | M-57 | 0.12 | A-16 | 0.05 |
| 13 (Invention) | M-58 | 0.2 | A-16 | 0.1 | M-58 | 0.12 | A-16 | 0.05 |
| 14 (Invention) | M-59 | 0.2 | A-11 | 0.09 | M-59 | 0.12 | A-11 | 0.05 |
[0051] Each sample was exposed to white light through an optical wedge for 1/100 seconds, and subjected to the following Processing.
| Processing (38°C) | |
| Color developing | 3 min. 15 sec. |
| Bleaching | 6 min. 30 sec. |
| Washing | 3 min. 15 sec. |
| Fixing | 6 min. 30 sec. |
| Washing | 3 min. 15 sec. |
| Stabilizing | 1 min. 30 sec. |
| Drying | |
[0052] The composition of each processing liquid is as follows:
| Color developer | |
| 4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)-aniline sulfate | 4.75 g |
| Sodium sulfite anhydrous | 4.25 g |
| Hydroxylamine 1/2 sulfate | 2.0 g |
| Potassium carbonate anhydrous | 37.5 g |
| Potassium bromide | 1.3 g |
| Trisodium nitrilotriacetate (monohydrate) | 2.5 g |
| Potassium hydroxide | 1.0 g |
| Water wa added to make a total quantity 1ℓ (pH=10.2) | |
| Bleacher | |
| Ferric ammonium ethylenediaminetetraacetate | 100.0 g |
| Diammonium ethylenediaminetetraacetate | 10.0 g |
| Ammonium bromide | 150.0 g |
| Glacial acetic acid | 10 mℓ |
| Water was added to make a total quantity 1ℓ and pH was adjusted to 6.0 with aqueous ammonia. | |
| Fixer | |
| Ammonium thiosulfate | 175.0 g |
| Ammonium sulfite anhydrous | 8.5 g |
| Sodium metasulfite | 2.3 g |
| Water was added to make a total quantity 1ℓ and pH was adjusted to 6.0 with acetic acid. | |
| Stabilizer | |
| Formalin (37% solution) | 1.5 mℓ |
| Konidax (manufactured by Konica Corp) | 7.5 mℓ |
| Water was added to make a total quantity 1ℓ. | |
[0053] Graininess was evaluated in terms of RMS value. An RMS value was determined by a standard deviation of a variation of a density, which was observed when scanning a portion of 250 µm² on a magenta dye image having the density of the minimum density + 0.5 with a Sakura microdensitometer (model PDM-5, Type AR, manufactured by Konica Corp), and expressed by a value relative to that of Sample No. 1, which was set at 100.
[0054] Processing stability was evaluated by varying pH of the developer from 10.0 to 10.4 and observing a variation of a gamma value on the characteristic curve of a magenta dye image.
[0055] The gamma value variation is defined by the following equation, wherein A and B are the gamma values at pH 10.4 and 10.0 respectively:
Gamma value variation=(B/A-1) x 100
[0056] The smaller this value, the smaller the difference in gamma value. The results are shown in Table 2.
Table 2.
| Sample No. | Graininess | Processing stability |
| 1 (Comparison) | 100 | 25 |
| 2 (Comparison) | 92 | 36 |
| 3 (Comparison) | 93 | 35 |
| 4 (Invention) | 89 | 20 |
| 5 (Invention) | 83 | 15 |
| 6 (Invention) | 86 | 16 |
| 7 (Invention) | 89 | 18 |
| 8 (Invention) | 87 | 17 |
| 9 (Invention) | 85 | 15 |
| 10 (Invention) | 86 | 16 |
| 11 (Invention) | 82 | 13 |
| 12 (Invention) | 87 | 17 |
| 13 (Invention) | 81 | 14 |
| 14 (Invention) | 83 | 13 |
[0057] As is evident from the results, the samples of the invention are significantly improved in graininess and processing stability.
Example 2
[0058] The layers of the following constitutions were provided on a polyethylene-laminated paper support in sequence from the support to prepare Sample No. 15
| 1st Layer: blue-sensitive layer | |
| Silver chlorobromide emulsion (silver chloride content: 99.3 mol%) | 0.32 |
| Yellow coupler (Y-3) | 0.8 |
| High boiling solvent (Oiℓ-1) | 0.5 |
| Gelatin | 1.2 |
| 2nd Layer: anti-irradiation layer | |
| Anti-irradiation dye (AI-1) | 0.03 |
| Anti-irradiation dye (AI-2) | 0.02 |
| Gelatin | 0.7 |
| 3rd Layer: green-sensitive layer | |
| Silver chlorobromide emulsion (silver chloride content: 99.7 mol%) | 0.25 |
| Magenta coupler (M-56) | 0.6 |
| High boiling solvent (Oiℓ-1) | 0.3 |
| Gelatin | 1.25 |
| 4th Layer: interlayer | |
| Gelatin | 1.02 |
| 5th Layer: red-sensitive layer | |
| Silver chlorobromide emulsion (silver chloride content: 99.7%) | 0.3 |
| Cyan coupler (C-3) | 0.9 |
| High boiling solvent (Oiℓ-1) | 0.5 |
| Gelatin | 1.2 |
| 6th Layer: UV absorbing layer | |
| UV absorber (UV-3) | 0.3 |
| High boiling solvent (Oiℓ-1) | 0.2 |
| Gelatin | 1.0 |
| 7th Layer: protective layer | |
| Gelatin | 0.5 |
[0059] Sodium 4-dichloro-6-hydroxy-s-triazine was added as a hardener to each of the 2nd, 4th and 7th layers in an amount of 0.017 g per gram of gelatin.
[0060] Samples No. 16 to 19 of the invention were prepared in the same manner as above, except that the magenta coupler was replaced as shown in Table 3 and that Compounds A-I were added.
[0061] Each sample was exposed in the same manner as in Example 1 and subjected to the following processing, in which pH of the developer was varied from 10.0 to 10.4 to evaluate processing stability in the same manner as in Example 1.
| Processing | ||
| Temperature | Time | |
| Color developer | 34.7 ± 0.3°C | 45 sec |
| Bleach-fixing | 34.7 ± 0.5°C | 50 sec |
| Stabilizing | 30 to 34°C | 90 sec |
| Drying | 60 to 80°C | 60 sec |
| Color developer | |
| Pure water | 800 mℓ |
| Triethanolamine | 8 g |
| N,N-diethylhydroxylamine | 5 g |
| Potassium chloride | 2 g |
| N-ethyl-N-β-methanesulfonamidethyl-3-methyl-4-aminoaniline sulfate | 5 g |
| Sodium tetrapolyphosphate | 2 g |
| Potassium carbonate | 30 g |
| Potassium sulfite | 0.2 g |
| Fluorescent bleaching agent (4,4-diaminostilbene disulfonic acid derivative) | 1 g |
| Water was added to make a total quantity 1ℓ. | |
| Bleach-fixer | |
| Ferric ammonium ethylenediaminetetraacetate dihydrate | 60 g |
| Ethylenediaminetetraacetic acid | 3 g |
| Ammonium thiosulfate (70% solution) | 100 mℓ |
| Ammonium sulfite (40% solution) | 27.5 mℓ |
| Water was added to make a total quantity 1ℓ and pH as adjusted to 5.7 with potassium carbonate or glacial acetic acid. | |
| Stabilizer | |
| 5-Chloro-2-methyl-4-isothiazoline-3-one | 1 g |
| 1-Hydroxyethylidene-1,1-diphosphonic acid | 2 g |
| Water was added to make a total quantity 1ℓ, and pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide. | |
Table 3
| Sample No. | Coupler | Compound A-I | Processing stability | ||
| No. | Amount | No. | Amount | ||
| 15 (Comparison) | M-56 | 0.6 | - | - | 45 |
| 16 (Invention) | M-56 | 0.6 | A-3 | 0.3 | 25 |
| 17 (Invention) | M-56 | 0.6 | A-16 | 0.3 | 19 |
| 18 (Invention) | M-56 | 0.6 | A-19 | 0.3 | 21 |
| 19 (Invention) | M-60 | 0.6 | A-17 | 0.3 | 20 |
1. A silver halide light-sensitive photographic material comprising
a support and provided thereon plural and light-sensitive layers including
at least one green-sensitive layer
wherein the at least one green-sensitive layer contains a magenta coupler represented by Formula M-I and a compound represented by Formula A-I:
wherein Z represents the group of non-metallic atoms for forming a nitrogen-containing heterocyclic ring; X represents a hydrogen atom or a substituent capable of splitting off by a reaction with an oxidation product of a developer; and R represents a hydrogen atom or a substituent;
Formula A-I
H O (̵J)̵ C O O Y
wherein J represents a divalent organic group; Y represents an alkyl group, a cycloalkyl group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkenyl group and a heterocycilc group.
a support and provided thereon plural and light-sensitive layers including
at least one green-sensitive layer
wherein the at least one green-sensitive layer contains a magenta coupler represented by Formula M-I and a compound represented by Formula A-I:
wherein Z represents the group of non-metallic atoms for forming a nitrogen-containing heterocyclic ring; X represents a hydrogen atom or a substituent capable of splitting off by a reaction with an oxidation product of a developer; and R represents a hydrogen atom or a substituent;
Formula A-I
H O (̵J)̵ C O O Y
wherein J represents a divalent organic group; Y represents an alkyl group, a cycloalkyl group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkenyl group and a heterocycilc group.
2. The photographic material of claim 1, wherein the organic group represented by
J is an alkylene group an alkenylene group, a cycloalkylene group, a carbonyl group,
a carbonyloxy group, an arylene group and a heterocyclic group.
3. The photographic material of claim 2, wherein the organic group is an arylene group.
4. The photographic material of claim 3, wherein the organic group is a phenylene
group.
5. The photographic material of claim 1, wherein the groups represented by Y excluding
a heterocyclic group have 1 to 32 carbon atoms.
6. The photographic material of claim 1, wherein the heterocyclic group represented
by Y is a nitrogen-containing heterocyclic group.
7. The photographic material of claim 6, wherein the nitrogen-containing heterocyclic
group is pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrrolinyl, imidazolidinyl, piperadinyl
and piperidinyl.
8. The photographic material of claim 1, wherein an addition amount of the compound
represented by Formula A-I is 0.01 to 10 g/g of a magenta coupler.
9. The photographic material of claim 8, wherein the addition amount is 0.1 to 3.0
g/g of a magenta coupler.
10. The photographic material of claim 1, wherein the substituent represnted by R
is an alkyl group, an aryl group, an anilino group, an acylamino group, a sulfonamide
group, an alkylthio group, an arylthio gruop, an alkenyl group, a cycloalkyl group,
a halogen atom, a cycloalkenyl group, an alkynyl group, a heterocyclic group, a sulfonyl
group, a sulfinyl group, a phosphonyl group, an acyl group, a carbamoyl group, a sulfamoyl
group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclicoxy group,
a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkylamino
group, an imido group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino
group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl
group, a heterocyclicthio group, a spiro compound residue, or a bridged hydrocarbon
residue.
11. The photographic material of claim 1, wherein the group represnted by X is an
alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a sulfonyloxy
group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy
group, an alkoxyoxalyloxy group, an alkylthio group, an arylthio group, a heterocyclicthio
group, an alkoxythiocarbonylthio group, an acylamino group, a sulfonamide group,
a nitrogen-containing heterocyclic group having a bonding site at the nitrogen atom,
an alkoxycarbonylamino group, an aryloxycarbonylamino group, a carboxyl group, and
wherein R₁′ans Z′ are the same as those defined for R an Z, respectively; and R₂′ and R₃′ represent independently a hydrogen atom, an alkyl group, an aryl group and a heterocyclic group.
wherein R₁′ans Z′ are the same as those defined for R an Z, respectively; and R₂′ and R₃′ represent independently a hydrogen atom, an alkyl group, an aryl group and a heterocyclic group.
12. The photographic material of claim 1, wherein the nitrogen-containing heterocyclic
ring formed by Z is a pyrazole ring, an imidazole ring, a triazole ring and tetrazole
ring.
13. The photographic material of claim 1, wherein the magenta coupler is represnted
by one of Formulas M-II to M-VII:
wherein R₁ to R₈ and X are the same as those defined for R and X in Fromula M-I, respectively.
wherein R₁ to R₈ and X are the same as those defined for R and X in Fromula M-I, respectively.
14. The photographic material of claim 13, wherein the magenta coupler is represented
by Formula M-II.
15. The photographic material of claim 13, wherein R₂ to R₆ represent independently
a group represented by Formula IX:
wherein R¹ represents an alkylene group; R² represents an alkyl group, a cycloalkyl group or an aryl group.
wherein R¹ represents an alkylene group; R² represents an alkyl group, a cycloalkyl group or an aryl group.
16. The photographic material of claim 15, wherein R¹ or R² has at least one acid
group.
17. The photographic material of claim 16, wherein the acid group is a carboxylic
group or a sulfonic group.
18. The photographic material of claim 17, wherein the acid group is a carboxylic
group or a salt thereof.