JPH0754403B2 - Silver halide color photographic light-sensitive material containing a novel coupler - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material containing a novel coupler which releases a reducing agent capable of scavenging an oxidized color developing agent by a coupling reaction.

BACKGROUND OF THE INVENTION In recent years, research on high sensitivity and high image quality of silver halide color photographic light-sensitive materials has overcome the contradictory problems of high sensitivity and high image quality as seen in ISO1600 color film, and has achieved great results. As mentioned above, in addition to advanced control of silver halide grain growth and advancement of sensitization technology, functional materials such as highly reactive 2-equivalent carapoo and development inhibitor releasing coupler (DIR coupler) have been mentioned. Has played an important role.

However, it is known that a highly reactive 2-equivalent coupler, which is indispensable for increasing the sensitivity, deteriorates image quality, particularly graininess.

Further, the use amount of the DIR coupler, which improves the image quality by suppressing the development of silver halide grains, causes a decrease in sensitivity, and therefore the amount used is limited. Therefore, under the present circumstances, it is difficult to further advance the goal of simultaneously improving high sensitivity and high image quality by improving only conventional techniques. After the coupling reaction there,
Couplers which produce a mobile dye and apparently improve the graininess have been proposed in JP-A-57-82837, 57-17950, etc., but sharpness deterioration and graininess due to dye migration are proposed. The improvement is at the same level and cannot be an essential improvement in image quality.

In addition, JP-A-56-135841, JP-A-56-133734, U.S. Pat.
No. 4,310,618, RD (Research Disclosure) 1
No. 9,633 discloses a blocked coupler in which an image forming coupler is protected by a colorless coupler or a coupler soluble in a developing solution. These couplers not only consume the amount of color developing agent oxidant required for image formation,
It also has the ability to scavenge an excess of oxidized color developing agent, which is advantageous for graininess because it prevents the densification of the dye cloud due to the high reactivity as seen in a usual 2-equivalent coupler. Since the image-forming coupler is released after the coupling reaction of the protective coupler, the sensitivity is remarkably lowered and it is not suitable for high sensitivity.

If only scavenging the oxidized color developing agent is used
-72158, 59-5247, 58-156932, etc., anti-fouling agents and white couplers described in British Patent No. 1,284,649 may be used, but they are uniform regardless of the exposure dose. Since it is distributed in, the sensitivity is lowered. Therefore, only a very small amount can be used in the silver halide emulsion layer and an image quality improving effect cannot be expected.

On the other hand, a coupler that scavenges an oxidized color developing agent to form a fine dye cloud by competitively reacting an oxidized color developing agent with an image forming coupler to form a fine dye cloud is disclosed in British Patent No. 1,546,837, JP-A-52-150631. No. 57-111537, etc., but the scavenging ability is low and a sufficient image quality improving effect cannot be obtained.

In addition, JP-A-57-138636, 61-53643, 61-84646
No. 61-86751, No. 61-102646, No. 61-102647, No. 61-102647
Nos. 61-107245 and 61-113060 disclose a coupler capable of forming a finer and more uniform dye cloud without image-wise release of a reducing agent capable of scavenging an oxidized product of a color developing agent without image sensitivity reduction. However, since the exemplified compounds described are still low in scavenging ability and the scavenger release rate is not sufficient, a reducing agent releasing coupler having a higher scavenging ability has been desired. Further, desensitization and contamination of the photosensitive silver halide emulsion by incorporating the reducing agent in the light-sensitive material are also problems, and a more stable reducing agent-releasing coupler has been desired.

OBJECT OF THE INVENTION An object of the present invention is to include a novel coupler which releases a reducing agent at a sufficient rate, which is stable during storage and has a high ability to scavenge an oxidized color developing agent during development. An object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in sensitivity, high in sensitivity, and less polluting.

[Constitution of Invention] The above object of the present invention is achieved by a silver halide color photographic light-sensitive material containing a coupler represented by the following general formula [Ia], [Ib] or [Ic].

General formula [Ia] General formula [Ib] General formula [Ic] In the formula, A is coupled with the oxidized developing agent and then,
Represents a coupler residue that releases a group other than A, TIME represents a timing group that releases a portion other than TIME after leaving from A by a coupling reaction, and n is 0 or 1
X and Y represent a nitrogen atom or a substituted or unsubstituted methine group, Z represents an oxygen atom, a sulfur atom,
Represents a selenium atom or SO ₂ , W is an OH group, —NHSO ₂ R
Group, NH ₂ group, NH-R group, Represents an NHCOR group, wherein R and R'represent an optionally substituted alkyl group, an arule group or a heterocyclic group. Further, X and Y or Y and W (when R is included) may be connected to each other to form a cyclic structure.

[Specific Structure of the Invention] The coupler represented by the general formula [Ia], [Ib] or [Ic] will be described.

The coupler residue represented by A is a yellow coupler residue, a magenta coupler residue, a cyan coupler residue or a substantially colorless coupler residue, preferably represented by the following general formulas [II] to [VIII]. It is a coupler residue.

General formula [II] General formula [III] General formula [IV] General formula [V] General formula [VI] General formula [VII] General formula [VIII] In the formula, R ₄ represents an alkyl group, an aryl group or an arylamino group. R ₅ represents an aryl group, preferably a phenyl group. R ₆ represents an alkyl group or an aryl group. R ₇ represents an alkyl group, an acylamino group, an arylamino group or a ureido group. R ₈ is an acylamino group,
It represents an alkylsulfonamide group, an alkyl group or an alkoxy group. R ₉ represents an alkyl group or an aryl group. R ₁₀ represents an acylamino group, a carbamoyl group or a ureido group. R ₁₁ represents an alkyl group, an alkoxy group, a halogen atom or an acylamino group. R ₁₂ represents a substituted amino group, an acylamino group, a carbonic acid amino group, a sulfonamide group or a hydroxyl group. l represents an integer of 0 to 2. k represents 0 or 1.

Each group represented by R _{4 to} R ₁₂ also includes those having a substituent, and preferable examples of the substituent include a halogen atom, a nitro group, a carboxyl group, an alkoxy group, a sulfonamide group, an alkyl group and an aryl group. To be

The timing group represented by TIME in the general formulas [Ia], [Ib] and [Ic] is used for the purpose of adjusting the coupling rate and the diffusibility of the group linked to the timing group. May or may not be used.

As a timing group represented by TIME, U.S. Pat.
No. 962, JP-A-57-56837, etc., in which a photographically useful group is eliminated by an intramolecular nucleophilic substitution reaction after elimination from A by a coupling reaction, British Patent 2,072,363.
No. 5, JP-A-57-154234, JP-A No. 57-188035, etc., which leaves a photographically useful group by electron transfer through a conjugated system, and aromatic group No. 1 as disclosed in JP-A-57-111536. Examples thereof include those which are coupling components capable of leaving a photographically useful group by a coupling reaction with an oxidized product of a primary amine developer.

X and Y in the general formulas [Ia], [Ib] and [Ic]
When represents a methine group, the methine group may have a substituent. As the substituent, for example, a substituted or unsubstituted, linear or branched, straight or branched chain having 1 to 22 carbon atoms,
A saturated or unsaturated alkyl group (eg, methyl group, i
-Propyl group, t-butyl group, cyclohexyl group, dodecyl group, butenyl group, benzyl group, methoxymethyl group, etc.), a substituted or unsubstituted aryl group (e.g., phenyl group, 4-carboxyphenyl group, mesityl group, etc., Preferably a phenyl group), a heterocyclic group (for example, a 2-benzthiazolyl group, a 2-imidazolyl group, a 2-benzoxazolyl group, a 1-phenyl-5-tetrazolyl group, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group). Group, butoxy group etc.), alkylthio group (eg methylthio group, dodecylthio group etc.), carbamoyl group (eg carbamoyl group, dimethylcarbamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, octyloxycarbonyl group etc.) ), An arylthio group (for example, a phenylthio group, 4-dode Luoxyphenylthio group etc.), acylamino group (eg acetylamino group, benzoylamino group etc.), sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group etc.), ureido group (eg methylureido group, Phenylureido group etc.), alkoxycarbonylamino group (eg methoxycarbonylamino group etc.), aryloxycarbonylamino group (eg phenoxycarbonylamino group etc.), sulfamoylamino group (eg dimethylsulfamoylamino group etc.) ), An amino group (for example, an amino group, a methylamino group, a dodecylamino group, a diethylamino group, an anilino group, etc.), an aryloxy group (for example, a phenoxy group, etc.), a hydroxyl group, a carboxyl group, a mercapto group, a halogen atom (for example, , Fluorine Child, such as chlorine atom), an acyl group (e.g., acetyl group, benzoyl group).

In the general formulas [Ia], [Ib] and [Ic], when R or R'represents an alkyl group, the alkyl group has 1 to 22 carbon atoms, and is a substituted or unsubstituted chain or cyclic group.
It may be linear or branched, saturated or unsaturated. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, a hydroxyl group, an acyloxy group,
Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, alkylamino group, anilino group, acylamino group, sulfonamide group, alkoxycarbonylamino group, ureido group, carbamoyl group, carboxyl group, sulfamoyl group, sulfonyl group, alkylthio Group, arylthio group, sulfo group, nitro group and cyano group.

When R or R'in the general formulas [Ia], [Ib] and [Ic] represents an aryl group, the aryl group is preferably a phenyl group, and examples of the substituent include an alkyl group of R or R '. The same as the substituents that can be possessed can be mentioned.

When R or R'in the general formulas [Ia], [Ib] and [Ic] represents a heterocyclic group, the heterocycle is a 5- or 6-membered heterocyclic group containing an oxygen atom, a sulfur atom or a nitrogen atom. preferable. Examples thereof include pyrazole, imidazole, 1,2,4-triazole, benzimidazole, pyridine, pyrimidine and indole.

Of the couplers represented by the general formulas [Ia], [Ib] and [Ic], the most preferable couplers are those represented by the following general formula [Id] or [Ie].

General formula [Id] General formula [Ie] In the formula, R ″ represents a substituent.

Next, examples of the couplers represented by the general formulas [Ia], [Ib] and [Ic] of the present invention are shown.

<Compound> Synthesis Example 1 Synthesis of DSR-1 To 19.2 g of (1) synthesized by the method described in J. Cehm. Soc. 1443 (1949), 100 ml of pyridine was added, and 11.5 g of methanesulfonyl chloride was added dropwise thereto. After dropping, the mixture was stirred for 1 hour, and the reaction solution was poured into ice water. The precipitated solid was filtered, washed with water and dried to obtain 20.9 g of (2). Yield 94
%.

Next, 2.2 g of (2) and 6.1 g of (3) were dissolved in 100 ml of ethyl acetate, 1.0 g of triethylamine was added, and the mixture was heated under reflux for 3 hours. The reaction solution was poured into water and the ethyl acetate layer was extracted. This was concentrated under reduced pressure, and the residue was purified by silica gel chromatography to obtain 5.6 g of DSR-1. Yield 67
%.

The structure of this product was identified by elemental analysis and various spectral data.

Elemental analysis value C (%) H (%) N (%) S (%) Cl (%) Calculated value 61.52 6.60 6.68 7.64 4.22 Measured value 61.68 6.82 6.42 7.60 4.15 Synthesis example 2 Synthesis of DRS-22 (1) 5.8 g and Chemical Abstracts 40 4059 synthesized by a method similar to the method described in JP-A-50-123341.
1.7 g of (2) synthesized by the method described in (1946) was dissolved in 100 ml of dimethylformamide, and a solution prepared by dissolving 0.42 g of sodium hydroxide in 5 ml of water was added thereto, and the mixture was reacted for 1 hour. The reaction solution was poured into ice water, and the precipitated solid was filtered, washed with water and dried to obtain 6.5 g of (3). Yield 92
%.

Next, 100 ml of tetrahydrofuran and 1 g of palladium carbon were added to 6.5 g of (3) and hydrogenation was carried out at atmospheric pressure. When the reduction is complete, 0.73 g of pyridine and butanesulfonyl chloride
1.44 g was added and reacted for 1 hour. The reaction solution was poured into water and extracted with ethyl acetate. This was concentrated under reduced pressure and the residue was purified by silica gel chromatography to obtain DSR-22.
5.1g was obtained. Yield 78% The structure of this product was identified by elemental analysis and various spectral data.

Elemental analysis value C (%) H (%) N (%) S (%) Cl (%) Calculated value 59.35 7.11 5.93 9.05 5.01 Measured value 59.19 6.89 6.03 9.08 5.15 The coupler of the present invention comprises a blue-sensitive emulsion layer and a green light-sensitive layer. Emulsion layer,
It can be contained in any layer such as a protective layer and an intermediate layer in addition to the red photosensitive emulsion layer, but it is preferably contained in at least one photosensitive emulsion layer.

The couplers of the present invention may be used alone or in combination of two or more. The amount of the coupler of the present invention used is 1 × 10 ⁻⁴ to 1 mol, preferably 0.005 to 0.1 mol, per mol of silver halide.

Further, the coupler of the present invention may be used in combination with a coupler other than the present invention, in which case the coupler outside the present invention is 0.01 to 100 moles, preferably 0.5 to 10 moles per mole of the coupler of the present invention.
Used in moles.

In order to incorporate the coupler of the present invention into a silver halide photographic light-sensitive material, various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water type emulsion dispersion method can be used. For example, in the oil-in-water emulsion dispersion method, the coupler is usually used in a high-boiling organic solvent having a boiling point of about 150 ° C or higher (for example, phthalic acid ester, phosphoric acid ester, etc.), if necessary, low boiling point, and / or water-soluble. It may be dissolved in an organic solvent in combination, emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution with a surfactant, and then added to the desired hydrophilic colloid layer.

The silver halide color photographic light-sensitive material of the present invention is usually supported by a silver halide emulsion layer and a non-light-sensitive layer containing magenta, yellow and cyan couplers as photographic couplers in order to perform color reproduction by subtractive method. Although it has a structure in which it is laminated on the body in an appropriate number of layers and layer order, the number of layers and layer order may be appropriately changed depending on the priority performance and the purpose of use.

The silver halide used in the silver halide color photographic light-sensitive material of the present invention is used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of the above can be used.

The silver halide emulsion used in the present invention is a sulfur sensitizing method,
It is chemically sensitized by a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method or the like.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry.

The silver halide color photographic light-sensitive material of the present invention includes an image stabilizer, an antifoggant, a hardener, a plasticizer, a latex, a surfactant, a color antifoggant, an ultraviolet absorber, a matting agent,
Additives such as lubricants and antistatic agents can be optionally used.

The silver halide color photographic light-sensitive material of the present invention can be subjected to various color development treatments to form a dye image.

Example 1 A multilayer color photographic element was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Unless otherwise specified, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² . Also, silver halide and colloidal silver are shown in terms of silver.

Sample-1 (Comparative) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver Second layer: Intermediate layer (IL) 2,5-Di-t-octylhydroquinone emulsified dispersion Gelatin layer Third layer: Low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Monodisperse emulsion (Emulsion I) consisting of AgBrI containing 0.30 μm average particle size (), 6 mol% AgI. g / m ² Sensitizing dye I: 6 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1): Silver 0.06 mol to 1 mol Colored cyan coupler (CC-1) ... 0.003 mol to 1 mol of silver DIR compound (D-1) ... 0.0015 mol to 1 mol of silver DIR compound (D-2) ... ... 0.002 mol per mol of silver 4th layer; high-sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size () 0.5 μm, AgBr containing 7.0 mol% AgI Monodisperse emulsion consisting of I (emulsion II): Silver coating amount 1.3 g / m ² Sensitizing dye I: 3 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II: against 1 mol of silver 1.0 × 10 ^-5 mol Cyan coupler (C-1) …… 0.02 mol per 1 mol silver Colored cyan coupler (CC-1) …… 0.0015 mol per 1 mol silver DIR compound (D-2) …… 0.001 mol per mol of silver Fifth layer; intermediate layer (IL) Same as the second layer, gelatin layer Sixth layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion I ... Silver coating amount 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol / mol of silver Sensitizing dye IV: 1.2 × 10 ^-5 mol / mol of silver Magenta coupler (M-1) 0.05 per mole of silver
0 mol Colored magenta coupler (CM-1) ... 0.009 mol to 1 mol of silver DIR compound (D-1) ... 0.0010 mol to 1 mol of silver DIR compound (D-3) ... to 1 mol of silver 0.0030 mol 7th layer; low-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion II …… Silver coating amount 1.4 g / m ² Sensitizing dye III …… 1.5 × 10 ⁻ per mol silver ⁵ mol Sensitizing dye IV: 1.0 × 10 ^-5 mol for 1 mol of silver Magenta coupler (M-1): 0.02 for 1 mol of silver
0 mol Colored magenta coupler (CM-1): 0.002 mol per mol of silver DIR compound (D-3): 0.0010 mol per mol of silver Eighth layer: Yellow filter layer (YC-1) Yellow A gelatin layer containing colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone Ninth layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Average particle size 0.48 μm, AgI 6 mol% Monodisperse emulsion consisting of AgBrI containing (Emulsion III) …… Silver coating amount 0.9g / m ² Sensitizing dye V …… 1.3 × 10 ^-5 mol per 1 mol of silver Yellow coupler (Y-1) …… Silver 0.29 per mole
Molar 10th layer: High-sensitivity blue-sensitive silver halide emulsion layer (BH-1) Monodisperse emulsion (Emulsion IV) consisting of AgBrI with an average grain size of 0.8 μm and AgI 5 mol% ... Silver coating amount of 0.5 g / m ² Sensitizing dye V: 1.0 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1): 0.08 per mol of silver
Mol DIR compound (D-2): 0.0015 mol per mol of silver 11th layer; first protective layer (Pro-1) silver iodobromide (AgI 1 mol% average particle size 0.07 μm) silver coating amount 0.5
g / m ² Gelatin layer containing UV absorbers UV-1 and UV-2 12th layer; 2nd protective layer (Pro-2) Polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1) Gelatin layer In addition to the above composition, gelatin hardener (H-1) is used for each layer.
And surfactants were added.

Half of the comparative coupler Y-1 in Layer 9 of Sample-1 was compared with comparative couplers Y-2, Y-3, Y-4, Y-5 and the exemplary compounds DSR-1, DSR-2, DSR-3 of the present invention. Sample-2 to 9 in the same manner as Sample-1 except that it was replaced with an equimolar amount of DSR-7.
It was created.

The compounds contained in each layer are as follows.

Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl-
3,3-Di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) Oxacarbocyanine hydroxide Sensitizing dye IV; Anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxy Thiacyanin Sensitometric exposure was applied to each of the samples thus prepared, and the following color development processing was performed.

The RMS granularity of the 0.8-density portion of the sample from which the dye image was obtained was scanned using a Sakura Microdensitometer PDM-5 type AR (manufactured by Konishi Rokushin Kogyo Co., Ltd.) using a 25 μ × 10 μ aperture. It was calculated as 1000 times the standard deviation of the fluctuation of the concentration value and is shown in Table-1.

Separately, each sample was adhered to a rectangular wave chart, exposed to a red color density of 1.0, and subjected to the above color development processing. The MTF of each spatial frequency of the obtained dye image sample was determined by the densitometer. Table 1 shows the MTF values at a spatial frequency of 50 lines / mm.

Further, the color image sample was stretched 10 times on a cherry color paper, color paper development processing (CPK-18P) was carried out, and the graininess was visually judged to evaluate the psychological graininess in grades 1 to 5. The larger the value, the better. Table of results
Shown in 1.

Treatment process (38 ℃) Color development phenomenon 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment liquid used in each treatment step is as follows. Is the street.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid / trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Water added 1 [bleaching solution] Ethylenediaminetetraacetic acid ammonium ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1 and adjust the pH to 6.0 with aqueous ammonia.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 and pH is adjusted to 6.0 with acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

As is clear from Table 1, Samples 6 to 9 using the coupler of the present invention have excellent RMS graininess and MTF sharpness and good print graininess, and it is clear that the image quality improving effect is excellent. . On the other hand, comparison couplers Y-2, Y-3, Y
Samples 2, 3 and 5 using -5 have almost no effect of improving the graininess and are considered to be close to an ordinary 2-equivalent coupler. Also, sample 4 using Y-4, which forms a mobile dye, apparently improves RMS graininess, but deteriorates the psychological graininess evaluated by printing, and not only does it not truly improve graininess. , MTF sharpness is significantly deteriorated.

Example 2 A multilayer color photographic element sample 10 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

First layer: Antihalation layer Gelatin layer containing black colloidal silver Second layer: Intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone Third layer: Low sensitivity red-sensitive silver halide emulsion Layer Emulsion (Emulsion I) consisting of AgBrI containing 4 μm AgI with an average grain size of 0.3 μm. Silver coating amount 0.5 g / m ² Sensitizing dye I: 7.9 × 10 ⁻⁴ mol cyan per 1 mol silver Coupler (C-2): 0.1 mol per 1 mol of silver Fourth layer: High-sensitivity red-sensitive silver halide emulsion layer Monodisperse emulsion consisting of AgBrI with average grain size 0.7 μm and AgI 3 mol% (Emulsion II) ) Silver coating amount 0.8 g / m ² Sensitizing dye I: 3.4 × 10 ^-4 mol per 1 mol of silver Cyan coupler (C-2): 0.2 mol per 1 mol of silver Fifth layer; intermediate layer (IL) same as the second layer, the gelatin layer 6th layer; low sensitivity green-sensitive silver halide emulsion layer emulsion I ...... silver laydown 1.0 g / m ² sensitizing dye III ... 1 mol of silver 2.9 × 10 ^-4 mol magenta coupler relative to 4.3 × 10 ^-4 mol sensitizing dye IV ...... 1 mol of silver relative to (M-1) 0.05 relative ...... silver mole
Molar 7th layer: High-sensitivity green-sensitive silver halide emulsion layer Emulsion II …… Silver coating amount 1.0 g / m ² Sensitizing dye III …… 1.8 × 10 ^-4 mol per 1 mol of silver Sensitizing dye IV …… 1.2 × 10 ⁻⁴ mol magenta coupler (M-1) for 1 mol silver ... 0.15 mol for 1 mol silver
Mol 8th layer; yellow filter layer gelatin layer containing yellow colloidal silver and emulsified dispersion of 2,5-di-t-octylhydroquinone 9th layer; low-sensitivity blue-sensitive silver halide emulsion layer average particle size 0.6 μm, AgBrI containing 3 mol% AgI Emulsion (Emulsion III) …… Silver coating amount 0.4 g / m ² Yellow coupler (Y-6) …… 0.3 against 1 mol of silver
Molar 10th layer: high-sensitivity blue-sensitive silver halide emulsion layer Emulsion (Emulsion IV) consisting of AgBrI containing 1.0 μm average grain size and 3 mol% AgI …… Silver coating amount 0.8 g / m ² Yellow coupler (Y-6) ) ... 0.3 for 1 mole of silver
Mol 11th layer; 1st protective layer Gelatin layer containing UV absorbers UV-1, UV-2 and 2,5-di-t-octylhydroquinone 12th layer; 2nd protective layer Silver iodobromide (AgI 1 mol %, Average particle size 0.06 μm) ... Silver coating amount 0.3 g / m ² and polymethylmethacrylate particles (diameter 1.5)
Gelatin layer containing μm) The compounds used to prepare Sample 10 are as follows.

The cyan coupler C of the third and fourth layers of the sample-10
-Samples 11 to 14 were prepared in the same manner as Sample-10, except that half of -2 was replaced with equimolar comparative couplers C-3 and C-4 and the exemplified compounds DSR-22 and DSR-23.

The obtained sample was subjected to the following color reversal development processing to obtain a color image.

RMS granularity (red density 1.0) and MTF sharpness (10 lines / mm) were determined in the same manner as in Example-1. The results are shown in Table-2.

Processing process Time Temperature 1st development 6 minutes 38 ℃ (± 0.3) Washing with water 2 minutes 38 ℃ (± 0.3) Inversion 2 minutes 38 ℃ (± 0.3) Color development 6 minutes 38 ℃ (± 0.3) Adjustment 2 minutes 38 ° C (± 0.3) Bleach 6 minutes 38 ° C (± 0.3) Settled 4 minutes 38 ° C (± 0.3) Washed in water 4 minutes 38 ° C (± 0.3) Stabilized 1 minute Room temperature dry First developing water 700 ml Tetrapolyphosphate Sodium 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-Phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water 1000ml Reverse water 700ml Nitrilo / N / N-trimethylenephosphonic acid / 6Na
Salt 3g Stannous chloride (dihydrate) 1g p-Aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water to 1000ml Color developing water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium triphosphate (dihydrate) Salt) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazinate 1.5g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 11g Ethylenediamine 3g Water was added to 1000ml Adjusted water 700ml Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Water was added 1000ml Bleached water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ethylenediaminetetraacetate Iron (III) ammonium (dihydrate) 120.0g Potassium bromide 100.0g Water is added 1.0l Fixing water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Bisulfite Sodium 5.0g Water added 1.0l Stable water 800ml Formalin (37% by weight) 5.0ml Surfactant solution (trade name: Conidax) 5.0ml Water added 1.0l Comparative Coupler As is clear from Table-2, samples using comparative couplers
10 to 12 have almost no improvement effect on both RMS graininess and MTF sharpness. On the other hand, samples 13 and 14 using the coupler of the present invention are RM
Greatly improves the S graininess and MTF sharpness.

Example-3 (Preparation of silver halide emulsion) Three types of silver halide emulsions shown in Table-3 were prepared by the neutral method and the simultaneous mixing method.

After the chemical sensitization, 5 × 10 ⁻³ mol of STB-1 shown below as an emulsion stabilizer was added to each silver halide emulsion per mol of silver halide.

(Preparation of silver halide color photographic light-sensitive material sample) Then, the following layers 1 to 7 are sequentially applied (simultaneous coating) on a paper support whose both sides are coated with polyethylene to prepare a silver halide color photographic light-sensitive material 15. did. (In the following examples, the addition amount is shown per 1 m ² of the light-sensitive material.) Layer 1 ... Gelatin (1.2 g) and 0.29 g (in terms of silver, the same applies hereinafter) of a blue-sensitive silver halide emulsion. (Em-1), and 0.
75g yellow coupler (Y-7), 0.3g light stabilizer ST
-1 and 0.015g of 2,5-dioctylhydroquinone (HQ
-1) A layer containing 3 g of dinonyl phthalate (DNP) dissolved therein.

Layer 2 ... Gelatin (0.9 g) and 0.04 g of HQ-1 dissolved
Layer containing 0.2 g DOP (dioctyl phthalate).

Layer 3: Gelatin (1.4 g), 0.2 g green light-sensitive silver halide emulsion (Em-2), 0.66 g of the following magenta coupler (M-2), 0.25 g of light stabilizer ST-2 and 0.01 g HQ−
0.5g of DOP in which 1 was dissolved and 6mg of the following filter dye AI-
A layer containing 1.

Layer 4: Gelatin (1.2 g) and 0.6 g of the following UV absorber
Layer containing 0.3 g DNP with UV-3 and 0.05 g HQ-1 dissolved.

Layer 5 Gelatin (1.4 g), 0.20 g of red-sensitive silver halide emulsion (Em-3), and 0.54 g of cyan coupler (C-5), 0.01 g of HQ-1 and 0.3 g of ST-. A layer containing 0.3 g of DOP with 1 dissolved.

Layer 6 ... Gelatin (1.1 g) and 0.2 g UV-3 dissolved.
A layer containing 2 g of DOP and 5 mg of the following filter dye AI-2.

Layer 7 ... Gelatin (1.0 g) and 0.05 g of 2,4-dichloro-6
A layer containing sodium hydroxytriazine.

In addition, the blue-sensitive silver halide emulsion (Em
-1) 0.32g (silver equivalent), yellow coupler (Y
The amount of -7) was reduced to 0.55 g, and the compound DSR-1 of the present invention was reduced to 0.
The same photosensitive material was used as photosensitive material 16 except that 49 g was added.

The obtained light-sensitive materials 15 and 16 were solid-exposed with red and green light using a sensitometer KS-7 type (manufactured by Konishi Roku Photo Industry Co., Ltd.) and solid-exposed with red and green light to obtain blue light. After processing the sample that was wedge-exposed with light according to the following color development processing steps, use an optical densitometer (PDA-65 type manufactured by Konishi Rokusha Kogyo Co., Ltd.) to determine the density of the blue, green, and red photosensitive emulsion layers. Λ _max
It measured using the interference filter which has a maximum in 440 nm, 540 nm, and 650 nm.

The photosensitive material 15 is subjected to solid exposure with red and green light, wedge exposure with blue light, and after color development processing, using an optical densitometer,
The results of measuring the densities of the blue, green and red photosensitive emulsion layers are shown in FIG. 1, and the photosensitive material 16 was subjected to solid exposure with red and green light, wedge exposure with blue light, and after color development processing, The results of measuring the densities of the blue, green and red photosensitive emulsion layers using an optical densitometer are shown in FIG.

In the figure, B indicates the density of the blue photosensitive emulsion layer, G indicates the density of the green photosensitive emulsion layer, and R indicates the density of the red photosensitive emulsion layer.

[Processing process] Temperature Time Color development 34.7 ± 0.3 ℃ 45 seconds Bleach fixing 34.7 ± 0.5 ℃ 50 seconds Stabilization 30 to 34 ℃ 90 seconds Dry 60 to 80 ℃ 60 seconds [Color developer] Pure water 800ml Triethanolamine 8g N, N-diethylhydroxyamine 5g Potassium chloride 2g N-ethyl-N-β-methanesulfonamide ethyl-3
-Methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Potassium sulfite 0.2g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1g Add pure water to make the total amount 1 and pH 10 Adjust to 2.

[Bleaching fixer] Ethylenediaminetetraacetic acid ferric ammonium dihydrate
60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 5.7 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one
1 g 1-Hydroxyethylidene-1,1'-diphosphonic acid 2 g Water is added to bring the total amount to 1, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

As is clear from FIG. 1, the clear interimage effect is not observed in the light-sensitive material 15, but as is clear from FIG. 2, the clear interimage effect is observed in the light-sensitive material 16 using the compound of the present invention. Is recognized.

[Brief description of drawings]

FIG. 1 shows that the photosensitive material 15 of Example 3 was subjected to solid exposure with green and red light, wedge exposure with blue light, and color development processing,
Use an optical densitometer to measure the densities of the blue (B), green (G), and red (R) photosensitive emulsion layers at λ _max 440 nm, 540 nm, and 650 n, respectively.
The figure which shows the result measured using the interference filter which has a maximum in m. FIG. 2 shows that the photosensitive material 16 of Example 3 was subjected to solid exposure with green and red light, wedge exposure with blue light, and color development processing,
Use an optical densitometer to measure the densities of the blue (B), green (G), and red (R) photosensitive emulsion layers at λ _max 440 nm, 540 nm, and 650 n, respectively.
The figure which shows the result measured using the interference filter which has a maximum in m.

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Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a coupler represented by the following general formula [Ia], [Ib] or [Ic]. General formula [Ia] General formula [Ib] General formula [Ic] In the formula, A is coupled with the oxidized developing agent and then,
Represents a coupler residue that releases a group other than A, TIME represents a timing group that releases a portion other than TIME after leaving from A by a coupling reaction, and n represents 0 or 1
X and Y represent a nitrogen atom or a substituted or unsubstituted methine group, Z represents an oxygen atom, a sulfur atom,
Represents a selenium atom or SO ₂ , W is an OH group, —NHSO ₂ R
Group, NH ₂ group, NH-R group, Represents an NHCOR group, in which R and R ′ each represent an optionally substituted alkyl group, aryl group or heterocyclic group. Further, X and Y or Y and W (when R is included) may be connected to each other to form a cyclic structure.