JPH07168328A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material good in sensitivity and sharpness and superior in color reproduction performance. CONSTITUTION:This photosensitive material contains in the photographic constituent layer a novel compound represented by formula I in which R<1> is II or a substituent; Cp is a coupler residue to be allowed to release the Time and the following groups by reaction with the oxidation product of a developing agent; L is one of groups represented by formula II; X is O, S, or=N-R<5>; Time is a timing group; PUG is a photographic useful group; each of 1, m, and n is an integer of 0-3; and each of R<2>-R<5> is H or a substituent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high sharpness and sensitivity and excellent color reproducibility.

[0002]

2. Description of the Related Art Conventionally, in the photographic industry, couplers which release a photographically useful group upon reaction with an oxidized product of a developing agent have been known. The photographically useful group is a development inhibitor, a development accelerator, a bleaching accelerator, a fogging agent, a dye, a fluorescent whitening agent, DP '.
For example, a scavenger. These photographically useful groups contribute to the improvement and stabilization of the image quality by being released imagewise or non-imagewise into the silver halide emulsion layer. In particular, many couplers that release a development inhibitor are known. For example, U.S. Pat. Nos. 3,227,554 and 3,148,062 and Journal of the American Chemical Society 72
Volume 1950, page 1533, describes couplers that release development inhibitors from the coupling position.

It is well known that it is important for these development inhibitor releasing couplers to control the expression of their effects temporally and distancewise in order to improve the sharpness and graininess of images. . Therefore, a coupler in which a photographically useful group is bonded to an active site through a timing group by intramolecular nucleophilic substitution reaction or electron transfer is US Pat. No. 4,248,962,
No. 4,409,323, No. 4,684,604, No. 4,409,323, and European Patent Publication No. 167,168.

However, the types of development inhibitor groups that can be released at a desired rate through these timing groups are limited, and further development inhibitor releasing couplers having a sufficient effect are desired.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material having good sensitivity and sharpness and excellent color reproducibility.

[0006]

The object of the present invention is to provide at least one hydrophilic colloid layer containing a compound represented by the following general formula (I), which is a silver halide photographic light-sensitive material. Achieved by the material.

[0007]

[Chemical 3]

In the formula, R ¹ represents a hydrogen atom or a substituent, and C
p represents a coupler residue capable of releasing a group of Time or less by reaction with an oxidized product of a developing agent, and L represents

[0009]

[Chemical 4]

Represents an oxygen atom, a sulfur atom or = N
Represents -R ^5, Time represents a timing group, PUG represents a photographically useful group. l, m, and n each represent an integer of 0 to 3. R ² , R ³ , R ⁴ , and R ⁵ each represent a hydrogen atom or a substituent.

In the above general formula (I), the photographically useful group represented by PUG is a photographic development inhibitor residue and / or is represented by Cp in the above general formula (I). A silver halide photographic light-sensitive material containing a compound in which a coupler residue is a residue that forms a yellow, magenta or cyan dye and a residue that forms a substantially colorless product is more remarkable.

The present invention will be described in detail below.

In the general formula (I), R ¹ represents a hydrogen atom or a substituent. The substituent represented by R ¹ is an alkyl group,
Aryl group, heterocyclic group, halogen atom, nitro group, hydroxy group, acyl group, sulfonyl group, alkoxycarbonyl group, cyano group, amino group, carbamoyl group, acylamino group, sulfonylamino group, carboxy group, alkoxy group, alkylthio group And the like. These substituents may further have another substituent.

Next, the timing group represented by Time in the general formula (I) will be described in detail. The timing group represented by Time in the general formula (I) is represented by the following general formula (I
It is represented by I) and (III).

[0015]

[Chemical 5]

In the general formula (II), W represents a benzene ring or a naphthalene ring which may have a substituent and is preferably a substituted or unsubstituted benzene ring.

The oxygen atom is bonded to the coupling position of the coupler residue represented by Cp in the general formula (I), and R ₁ is a hydrogen atom or an alkyl group (for example, methyl, ethyl, 2-cyanoethyl, hydroxyethyl). Etc.), cycloalkyl group (eg cyclohexyl, cyclopentyl, 4-chlorocyclohexyl etc.), alkenyl group (eg vinyl, propenyl etc.), alkynyl group (eg propargyl, butynyl etc.) or aryl group (eg phenyl, p-anisyl, 2 -
Naphthyl etc.) etc. R ₁ is preferably a hydrogen atom.

R ₂ is a fluorine atom, a cyano group, a nitro group, --C
_{OR 5, -SO 2 R 5,} -SOR 5, represents a -NR ₆ R _7. R ₅ represents a hydrogen atom or a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, an aryloxy group, an amino group, an alkylamino group, an arylamino group, a dialkylamino group, an acylamino group, a hydroxyl group, It represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl or the like. Preferred as R ₂ are a cyano group, an alkoxycarbonyl group and a carbamoyl group.

R ₆ and R ₇ represent a hydrogen atom or a substituent,
Examples of the substituent include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl and the like.

Further, -C (R ₁ ) (R ₂ )-is substituted at the ortho or para position with respect to the oxygen atom.

In the general formula (III), R ₁ and R ₂ have the same meanings as in the general formula (II). R ₄ is, for example, a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group or a heterocyclic group, and R ₃
Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, a carbamoyl group, a sulfonylamino group, a carboxyl group, an acylamino group, an alkoxycarbonyl group, or a cyano group.

Further, this timing group is bound to the coupling position of the coupler residue represented by Cp in the general formula (I) with an oxygen atom.

Time useful in the present invention is preferably represented by the following general formula (II-1), (II-2) or (III-1).

[0024]

[Chemical 6]

In the formula, R ₁ , R ₂ and R ₃ have the same meanings as in the general formulas (II) and (III). R ₀ represents a group capable of substituting on the benzene ring, for example, a halogen atom, a nitro group, a cyano group,
Acylamino group, sulfonamide group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, alkyl group, alkoxy group, aryloxy group, alkylamino group, Represents an acyl group and the like.

Of these, in terms of release rate (II-1)
And (II-2) are more preferable.

In the general formula (I), PUG represents a photographically useful group and includes, for example, a development inhibitor, a development accelerator, a bleaching accelerator, a fog agent, a dye, a fluorescent whitening agent, an auxiliary developing agent, an image forming coupler, Competing couplers, bleach inhibitors, silver halide solvents, silver complex salt forming agents, hardeners, DP 'scavengers, image stabilizers and the like can be mentioned. PUG preferred among these
Examples include development inhibitors, development accelerators, DP 'scavengers and dyes.

Specific examples of the development inhibitor include benzotriazole compounds, benzimidazole compounds, 1,2,3-triazole compounds, 1,2,4-triazole compounds, tetrazole compounds, mercaptoimidazole compounds, mercaptothiazole compounds, and mercapto. There are tetrazole compounds, mercaptothiadiazole compounds, mercaptooxadiazole compounds, mercaptotriazole compounds and the like. Specific examples of the auxiliary developer and the development accelerator include a pyrazolidone compound. Specific examples of DP 'scavengers include hydroquinone compounds, catechol compounds, pyrogallol compounds, aminophenol compounds,
Examples thereof include sulfonylaminophenol compounds and disulfonylaminophenol compounds.

The compound represented by Cp in the general formula (I) will be described in detail below, but it is bonded to-(Time) n- at the * -position. First, as the yellow coupler residue, those represented by the following general formulas (IV) and (V) are preferable.

[0030]

[Chemical 7]

In the above general formulas (IV) and (V),
R ₈ and R ₉ represent, for example, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or a halogen atom, and the alkyl group, the cycloalkyl group, the aryl group and the heterocyclic group include an oxygen atom, a nitrogen atom and a sulfur atom. You may couple | bond through an atom. Further, the alkyl group, cycloalkyl group, aryl group, and heterocyclic group may be bonded via a bonding group listed below. That is, carbonylamino, carbamoyl,
Sulfonamide, sulfamoyl, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone, sulfonyloxy groups, etc., and the alkyl group, cycloalkyl group, aryl group, and heterocyclic group are as follows. It may have a substituent described in.

That is, a halogen atom or nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxyl, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamide, Heterocycle, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxyl, imide, acyl groups and the like.

Each of R ₈ and R ₉ may be plural, and when each of R ₈ and R ₉ is 2 or more, they may be the same or different.

Examples of the magenta coupler residue represented by Cp in the general formula (I) include the following general formulas (VI) and (VI
Those represented by I), (VIII) and (IX) are preferred.

[0035]

[Chemical 8]

In the above general formulas (VI) to (IX),
R ₁₀ and R ₁₁ have the same meanings as R ₈ and R _{9 in} formulas (IV) and (V).

As the cyan coupler residue represented by Cp in the general formula (I), those represented by the following general formulas (X), (XI) and (XII) are preferable.

[0038]

[Chemical 9]

In the above general formulas (X) to (XII),
R ₁₂ and R ₁₃ have the same meanings as R ₈ and R _{9 in} formulas (IV) and (V).

As the coupler residue forming a substantially colorless product represented by Cp in the general formula (I), those represented by the general formulas (XIII) to (XVI) are preferable.

[0041]

[Chemical 10]

In the formula, R ₁₄ represents, for example, a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group or a heterocyclic group, and X represents an oxygen atom or ═NR ₁₅ . R ₁₅ represents an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or a sulfonyl group. Z is 5-7
Represents a group of non-metal atoms required to form a member carbocycle (eg, indanone, cyclopentanone, cyclohexanone, etc.) or a heterocycle (eg, piperidone, pyrrolidone, hydrocarbostyril, etc.).

[0043]

[Chemical 11]

In the formula, R ₁₆ and X are each represented by the general formula (XII
It has the same meaning as R ₁₄ and X in I), and R ₁₇ is an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylamino group, a dialkylamino group. Alternatively, it represents an anilino group.

[0045]

[Chemical 12]

In the formula, R ₁₈ and R ₁₉ may be the same or different, and examples thereof include an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group and ammonium. Mill base or

[0047]

[Chemical 13]

Represents F represents a group of non-metal atoms necessary for forming a 5- to 7-membered heterocycle (for example, phthalimide, triazole, tetrazole, etc.) with a nitrogen atom.

[0049]

[Chemical 14]

In the formula, R ₂₀ represents, for example, an alkyl group, an aryl group, an anilino group, an alkylamino group or an alkoxy group, and D represents an oxygen atom, a sulfur atom or a hydrogen atom or a nitrogen atom having a substituent.

In the general formula (I), L is

[0052]

[Chemical 15]

And m represents an integer of 0 to 3, and when m is 2 or 3, L may be the same or different, and R ² and R ³ are each a hydrogen atom or an alkyl group. , Aryl group, alkoxy group, acyl group, acylamino group,
It represents an alkoxycarbonyl group, a sulfonyl group, a carbamoyl group, a cyano group, a nitro group, a halogen atom and the like. or,
R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, a carbamoyl group or the like. Preferred-(L) m- is

[0054]

[Chemical 16]

And R ² , R ³ and R ⁴ are selected from a hydrogen atom, an alkyl group, an aryl group and the like.

X represents an oxygen atom, a sulfur atom or ═N—R ⁵ , and R ⁵ has the same meaning as R ⁴ . X is preferably an oxygen atom or a sulfur atom.

The typical examples of the compounds of the present invention are shown below, but the present invention is not limited thereto.

[0058]

[Chemical 17]

[0059]

[Chemical 18]

[0060]

[Chemical 19]

[0061]

[Chemical 20]

[0062]

[Chemical 21]

[0063]

[Chemical formula 22]

[0064]

[Chemical formula 23]

[0065]

[Chemical formula 24]

The compounds according to the present invention can be synthesized by methods known in the organic synthesis art. A specific synthesis example is shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound 1)

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

I) Synthesis of compound (3) 17.2 g of compound (2) was dissolved in 150 ml of acetone and 15.1 g of potassium carbonate was added. After adding 59.1 g of compound (1), the mixture was heated under reflux for 2 hours. After cooling, the precipitated inorganic salt was filtered off, and the filtrate was concentrated.

200 ml of ethyl acetate was added, and the mixture was washed twice with 100 ml of water. The crude product obtained by distilling off ethyl acetate under reduced pressure was recrystallized from ethyl acetate-hexane to obtain 61.1 g of compound (3).

Ii) Synthesis of compound (4) 43.1 g of compound (3) was dissolved in 150 ml of ethanol.

0.86 g of 5% palladium-carbon was added and the catalytic hydrogenation reaction was carried out under normal pressure. After the reaction was completed, palladium carbon was filtered off and the residue was distilled off under reduced pressure with ethanol to obtain 40.4 g of compound (4).

Iii) Synthesis of compound (5) 40 g of compound (4), 11.5 g of succinimide, formalin 9.
The mixture was heated under reflux with 5 ml in 200 ml of ethanol for 20 hours. After cooling, the reaction was poured into 1 l of water and 50 ml of ethyl acetate with stirring. After separating from the organic layer, it was dried over anhydrous magnesium sulfate. The crude product obtained by distilling off with ethyl acetate under reduced pressure was purified by silica gel chromatography to obtain 23.5 g of compound (5).

Iv) Synthesis of compound (6) 20 g of compound (5) was dissolved in 160 ml of dimethyl sulfoxide. With stirring, 1.1 g of sodium borohydride was added in small portions. After the addition was completed, the mixture was stirred at room temperature for 1 hour, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then with saturated saline. Obtained by distilling off ethyl acetate under reduced pressure.

The crude product was purified by silica gel chromatography to obtain 10.53 g of compound (6).

Synthesis of Exemplified Compound 1 7.02 g of compound (6) was dissolved in 35 ml of tetrahydrofuran. 3.83 g of compound (7) with stirring under a nitrogen atmosphere
Tetrahydrofuran solution (10 ml) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 3 hours, and then the reaction solution was added to ice water and extracted with ethyl acetate. It was washed with an ethyl acetate layer and brine and dried over anhydrous magnesium sulfate.

Ethyl acetate was distilled off under reduced pressure, and the obtained crude product was purified by silica gel chromatography.
The obtained crystals were recrystallized from ethyl acetate-hexane to give 3.52 g of Exemplified Compound 1 as colorless crystals.

The obtained compound was analyzed by Mass spectrum and NMR.
The structure was confirmed by the spectrum.

The compound according to the present invention can be contained in any layer of a photographic material, for example, a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer, but preferably in a silver halide emulsion layer. Good to use. More preferably, it is used for a red-sensitive silver halide emulsion layer and / or a blue-sensitive silver halide emulsion layer.

In order to incorporate the compound of the present invention into the hydrophilic colloid layer of a color light-sensitive material, for example, a known high-boiling solvent such as dibutyl phthalate, tricresyl phosphate and dinonylphenol and butyl acetate, propionic acid and the like are used. After dissolving the compound of the present invention alone or in combination in a mixed solution with a low boiling point solvent, it is mixed with a gelatin aqueous solution containing a surfactant, and then mixed with a high-speed rotary mixer or a colloid mill. Alternatively, it may be emulsified and dispersed using an ultrasonic disperser and then added directly into the emulsion, or after the above emulsified dispersion is set, it may be shredded and washed with water and then added to the emulsion.

The amount of the compound according to the present invention to be used is preferably 0.005 to 10 mol%, more preferably 0.01 to 5 mol% per mol of silver halide. The compound according to the present invention may be used alone or in combination of two or more.

As the silver halide emulsion used in the light-sensitive material of the present invention, any of ordinary silver halide emulsions can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color photographic light-sensitive material. Further, a color coupler having a color correcting effect, a competing coupler and a coupling agent with an oxidized product of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, Compounds that release photographically useful fragments such as fog agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development process may be contained.

A matting agent, a lubricant, an image stabilizer, a surfactant, an antifoggant, a development accelerator, a development retarder and a bleaching accelerator can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, a commonly known color photographic process can be carried out after exposure.

[0091]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

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

Example 1 A multi-layer color light-sensitive material sample 1 (comparative sample) 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 (HC) A gelatin layer containing black colloidal silver.

Second Layer: Intermediate Layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third Layer: Low-Sensitivity Red-Sensitive Silver Halide Emulsion Layer (RL) Monodisperse Emulsion (Emulsion I) 1.8 g Sensitizing Dye I 6 × 10 ^{− with an} average grain size of 0.30 μm and AgBr 6 containing 6 mol% of AgI. ⁵ mol / silver 1 mol Sensitizing dye II 1 × 10 ⁻⁵ mol / silver 1 mol Cyan coupler (C-1) 0.06 mol / silver 1 mol Colored cyan coupler (CC-1) 0.003 mol / silver 1 mol DIR compound ( D-1) 0.0035 mol / silver 1 mol Fourth layer: high-sensitivity red-sensitive silver halide emulsion layer (RH) Monodisperse emulsion (Emulsion II) 1.3 consisting of AgBrI containing 0.5 μm average grain size and 7.0 mol% AgI. g Sensitizing dye I 3 × 10 ^-5 mol / silver 1 mol Sensitizing dye II 1 × 10 ^-5 mol / silver 1 mol Cyan coupler (C-1) 0.02 mol / silver 1 mol Colored cyan coupler (CC-1) 0.0015 mol / silver 1 mol DIR compound (D-1) 0.001 mol / silver 1 mol Fifth layer: intermediate layer (IL) Same as second layer, gelatin Layer.

Sixth Layer: Low Sensitivity Green Sensitive Silver Halide Emulsion Layer (GL) Emulsion I 1.5 g Sensitizing Dye III 2.5 × 10 ⁻⁵ mol / silver 1 mol Sensitizing Dye IV 1.2 × 10 ⁻⁵ mol / silver 1 Mol Magenta coupler (M-1) 0.050 mol / silver 1 mol Colored magenta coupler (CM-1) 0.009 mol / silver 1 mol DIR compound (D-1) 0.0010 mol / silver 1 mol DIR compound (D-2) 0.0030 mol / Silver 1 mol Seventh layer: high-sensitivity green-sensitive silver halide emulsion layer (GH) emulsion II 1.4 g sensitizing dye III 1.5 × 10 ^-5 mol / silver 1 mol sensitizing dye IV 1.0 × 10 ^-5 mol / silver 1 mol Magenta coupler (M-1) 0.020 mol / silver 1 mol Colored magenta coupler (CM-1) 0.002 mol / silver 1 mol DIR compound (D-3) 0.0010 mol / silver 1 mol Eighth layer: yellow filter layer ( YC) Gelatin containing yellow colloidal silver and emulsified dispersion of 2,5-di-t-octylhydroquinone layer.

Ninth layer: low-sensitivity blue-sensitive silver halide emulsion layer (BL) Monodisperse emulsion (Emulsion III) 0.9 g Sensitizing dye V 1.3 × 10 ^{− with an} average grain size of 0.48 μm and AgBr 6 containing 6 mol% of AgI. ⁵ mol / silver 1 mol Yellow coupler (Y-1) 0.29 mol / silver 1 mol 10th layer: High-sensitivity blue-sensitive silver halide emulsion layer (BH) Average grain size 0.8 μm, consisting of AgBrI containing 15 mol% AgI Dispersion emulsion (Emulsion IV) 0.5 g Sensitizing dye V 1 × 10 ^-5 mol / silver 1 mol Yellow coupler (Y-1) 0.08 mol / silver 1 mol DIR compound (D-1) 0.0015 mol / silver 1 mol 11th Layer: First protective layer (Pro-1) Silver iodobromide (AgI 1 mol%, average particle size 0.07 μm) Gelatin layer containing ultraviolet absorbers (UV-1), (UV-2) 12th layer: 2nd Protective layer (Pro-2) Contains polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1) Keratin layer Incidentally, the respective layers in addition to gelatin hardener of the composition (H-
1) and a surfactant were added.

The compounds contained in each layer of the sample 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 (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'-methoxythiacyanine hydroxide

[0100]

[Chemical 27]

[0101]

[Chemical 28]

[0102]

[Chemical 29]

Further, the DIR compound (D-1) of the 10th layer of Sample 1 was replaced by equimolar amounts as shown in Table 1 below to prepare Samples 2 to 7.

[0104]

[Table 1]

[0105]

[Chemical 30]

Each of the samples 1 to 7 thus produced was subjected to wedge exposure using white light and processed in the following processing steps, and the sensitivity and fog of the blue photosensitive layer were measured.

In addition, the image sharpness was also measured. The sharpness was determined by determining the MTF of the dye image and using the relative value of the MTF at 30 lines / mm (Sample 1 being 100).

The results are shown in Table 1.

Treatment process (38 ° C) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Each treatment The composition of the treatment liquid used in the process is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline ・ sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine ・ 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitriloacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1 liter and add potassium hydroxide to p.
Adjust to H = 10.0.

[Bleach] Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Water was added to make 1 liter, and pH was adjusted with ammonia water.
Adjust to = 6.0.

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

[Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

From Table 1, it can be seen that the samples according to the present invention have significantly improved sharpness and high sensitivity.

Example 2 A basic sample was prepared by performing multilayer coating on the triacetate base in the following order. (1) Cyan coupler C-2 (same as in Example 1) 0.5
g, 2.4 g of gelatin and 1.6 g of silver halide, a red-sensitive silver iodobromide emulsion layer.

(2) A gelatin intermediate layer containing 0.5 g of gelatin and 0.1 g of 2,5-di-t-octylhydroquinone.

(3) Yellow coupler Y-1 (Example 1)
The same) 1.70 g, 2.4 g of gelatin, 1.6 g of silver halide, a blue-sensitive silver iodobromide emulsion layer.

(4) A protective layer made of 0.8 g of gelatin.

Among the constituent layers of the multilayer coating light-sensitive material described above, the following DIR couplers were added in the third layer containing a yellow coupler according to the addition amount as shown in Table 2 to prepare 5 kinds of samples 8 to 13. did.

[0120]

[Table 2]

[0121]

[Chemical 31]

Each sample was divided into two, one sample was subjected to wedge exposure with white light, and the other sample was subjected to wedge exposure with red light.

Then, the same treatment as in Example 1 was performed.

For each sample, the gamma value was obtained from the characteristic curve of the cyan dye obtained by color development, and the gamma by the red exposure (γ _R ) was changed to the gamma by the white exposure (γ _W ).
The values divided by are shown in Table 2.

As is clear from Table 2, the compounds of the present invention have a large γ _R / γ _w value, and a larger layering effect is obtained as compared with the case of using the conventional DIR coupler.

[0126]

According to the present invention, the sensitivity and the sharpness are good,
A silver halide photographic light-sensitive material excellent in color reproducibility was obtained.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one hydrophilic colloid layer containing a compound represented by the following general formula (I). [Chemical 1] In the formula, R ¹ represents a hydrogen atom or a substituent, Cp represents a coupler residue capable of releasing a group of Time or less by a reaction with an oxidized product of a developing agent, and L represents The stands, X represents an oxygen atom, a sulfur atom or = N-R ^5, Time represents a timing group, PUG represents a photographically useful group. l, m, and n each represent an integer of 0 to 3. R
² , R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent. 2. The silver halide photographic light-sensitive material according to claim 1, wherein in the general formula (I), the photographically useful group represented by PUG is a photographic development inhibitor residue. . 3. In the above general formula (I), the coupler residue represented by Cp is a residue that produces a yellow, magenta or cyan dye and a residue that produces a substantially colorless product. The silver halide photographic light-sensitive material according to claim 1 or 2, which is characterized.