JPH075646A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material high in sensitivity and superior in color reproduction performance and storage stability of a raw stock by incorporating a specified compound. CONSTITUTION:At least one of blue-sensitive silver halide emulsion layers contains at least one of the compounds represented by the formula: A2-(TM2)n2 IH2, and at least each one of green- and red-sensitive silver halide emulsion layers contains at least one of the compounds represented by the formula: A1-(TM1)n1-IH1. In the formulae, each of A1 and A2 is a coupler residue; each of TM1 and TM2 is a timing group combining with the coupler residue and released from the coupler residue by reaction with the oxidation product of a color developing agent and releasing IH1 and IH2, respectively, at a timing; n1 is 1, 2, or 3, and when n1 is 2 or 3, each of plural TM1 may be same or different; n2 is 0 or 1; and each of IH1 and IH2 is to be made a development inhibitor by each release.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having high sensitivity, excellent color reproducibility and sharpness, and excellent storage stability of raw samples. .

[0002]

2. Description of the Related Art In recent years, it has been strongly desired to develop a silver halide color photographic light-sensitive material having excellent color reproducibility and storability of raw samples. As a means for improving sharpness, D which reacts with an oxidized product of a color developing agent to release a development inhibitor
IR compounds are known. For example, U.S. Pat.
4, 3,701,783, 3,632,345, JP-A-49-7
The inhibitory group mercapto-type DIR compound described in 7635, etc. has a strong inhibitory effect in the layer and enables finer images, improved sharpness and gradation control, but an inhibitory effect on adjacent layers, so-called IIE. The effect was small and the color reproducibility was unsatisfactory.

Further, the DIR compounds having an azole-based inhibitor group as described in US Pat. No. 3,148,062, JP-A-49-122355, JP-A-52-82424 and JP-A-3-18844 are the above-mentioned mercapto compounds. It is possible to make edge effect and IIE effect larger than that of the compounds of the group
When the compound is added to the blue-sensitive layer and the triazole-based DIR compound is added to the green-sensitive layer and the red-sensitive layer, the IIE effect from the green-sensitive layer to the blue-sensitive layer and the IIE from the red-sensitive layer to the blue-sensitive layer are obtained. There was a problem that the effect was small.
Further, there is a drawback that self-layer desensitization becomes large when added in a large amount in order to obtain a sufficient IIE effect.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity, excellent color reproducibility, and excellent preservation of raw samples.

[0005]

The objects of the present invention are achieved by the following silver halide color photographic light-sensitive materials.

A blue-sensitive silver halide emulsion layer on a support,
In a silver halide color photographic light-sensitive material having a photographic constituent layer containing a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, at least one of the blue-sensitive silver halide emulsion layers has the following general formula [D- II] and at least one of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer contains at least one compound represented by the following general formula [D-I]. A silver halide color photographic light-sensitive material containing at least one kind.

General formula [D-I] A _1- (TIME ₁ ) n ₁ -INHIBIT ₁ [wherein A ₁ represents a coupler residue. TIME ₁ represents a timing group, is bonded to the coupling group A ₁ of the general formula [DI], and is cleaved from the coupler by the reaction with the oxidation product of the color developing agent, then sequentially cleaved, and finally To INH
Release IBIT ₁ with moderate control. n ₁ is 1 to 3, and when 2 and 3, each TIME ₁ may be the same or different. INHIBIT ₁ is a group which becomes a development inhibitor by the above release. ] Formula [D-II] _{A 2 - (TIME 2) n} 2 -INHIBIT 2 wherein, A ₂ represents a coupler residue. TIME ₂ represents a timing group, is bonded to the coupling group of A ₂ of the general formula [D-II], and is cleaved from the coupler by the reaction with the oxidized product of the color developing agent, and then sequentially cleaved to form the final compound. IN
HIBIT ₂ is released with moderate control. n ₂ is 0 or 1.

INHIBIT ₂ is a group which becomes a development inhibitor by the above release and is a triazole ring group represented by the following general formula [D-IIa] or general formula [D-IIb].

[0009]

[Chemical 2]

General formula [D-IIa] and general formula [D-II
b], R ₁ is an alkylthio group, R ₂ is H,
It is an alkyl group, an alkylthio group, an aryl group or a heterocyclic group. Substituents R ₁ and at least one R ₂ is a group -CO-OR _3, which can be hydrolyzed in aqueous alkali at a distance of 2-4 atoms from the triazole ring, -O-CO-OR ₃ or -CO-CO-, Contains R ₃ . R ₃ is an alkyl group, a cycloalkyl group, or an aryl group. The DIR compound represented by the general formula [DI] according to the present invention will be described below.

INHIBIT ₁ is a group serving as a development-inhibiting group, for example, a group represented by the general formula [D-2] to the general formula [D-9] and the general formulas [D-IIa] and [D-IIb]. .

[0012]

[Chemical 3]

In the general formulas [D-2] to [D-7], Rd ₁ is a halogen atom or alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolidinylideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N. -Alkylcarbamoyl, N,
N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocycle, cyano, alkylsulfonyl or aryloxycarbonylamino groups Represents

N ₁ represents 0, 1 or 2, and when n ₁ is 2, each Rd ₁ may be the same or different. General formula [D-
2] to General Formula [D-5] and General Formula [D-7], the total number of carbon atoms contained in Rd ₁ is 1 to 10,
In the general formula [D-6], the total number of carbon atoms contained in Rd ₁ is 0 to 15.

X in the above general formula [D-6] represents an oxygen atom or a sulfur atom.

In the general formula [D-8], Rd ₂ represents an alkyl group, an aryl group or a heterocyclic group.

In the general formula [D-9], Rd ₃ represents a hydrogen atom or an alkyl, cycloalkyl, aryl or heterocyclic group, and Rd ₄ represents a hydrogen atom, a halogen atom or alkyl, cycloalkyl, aryl or acylamino. Represents an alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamide, cyano, heterocycle, alkylthio or amino group.

The alkyl group in Rd ₁ , Rd ₂ , Rd ₃ or Rd ₄ includes those having a substituent and may be linear or branched.

The aryl group in Rd ₁ , Rd ₂ , Rd ₃ or Rd ₄ includes those having a substituent.

The heterocyclic group for Rd ₁ , Rd ₂ , Rd ₃ or Rd ₄ includes those having a substituent, and is a 5-membered compound containing at least one heteroatom selected from nitrogen atom, oxygen atom and sulfur atom, or A 6-membered monocyclic ring or condensed ring is preferable, and examples thereof include pyridyl, quinolyl, furyl,
Benzothiazolyl, oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide,
Each group of oxazine and the like can be mentioned.

In the general formula [D-8], the total number of carbon atoms contained in Rd _{2 is 0} to 15. In the general formula [D-9], the total number of carbon atoms contained in Rd ₃ and Rd ₄ is , 0
~ 15.

In the general formula [DI], TIME ₁ represents a timing group, and typical examples thereof include groups represented by the following general formulas [D-11] to [D-19].

[0023]

[Chemical 4]

In the general formula [D-11] to general formula [D-15] and general formula [D-18], Rd ₅ is hydrogen atom, halogen atom or alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl. , Anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl, carbamoyl, aryl,
Represents a carboxy, sulfo, hydroxy or alkanesulfonyl group. Rd ₅ is represented by the general formula [D-1
1] to general formula [D-13], general formula [D-15] and general formula [D-18], when l is 2 or more, Rd _{5 s} may bond to each other to form a condensed ring. Good.

In the general formula [D-11], general formula [D-14], general formula [D-15] and general formula [D-19], Rd ₆
Represents an alkyl, alkenyl, aralkyl, cycloalkyl, heterocycle or aryl group.

In the general formula [D-16] and general formula [D-17], Rd ₇ is a hydrogen atom or alkyl, alkenyl,
It represents an aralkyl, cycloalkyl, heterocyclic or aryl group.

In the general formula [D-19], Rd ₈ and Rd
d ₉ represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), and n ₂ represents an integer of ₂ to 4. A plurality of Rd ₈ and Rd ₉ may be the same or different.

In the general formulas [D-11] and [D-15] to [D-18], k represents an integer of 0, 1 or 2.

In the general formula [D-11] to general formula [D-13], general formula [D-15] and general formula [D-18], l is 1
Represents an integer of ~ 4.

In the general formula [D-16], m ₂ represents an integer of 1 or 2.

When l and m ₂ are 2 or more, Rd ₅ and Rd ₇
May be the same or different.

[0032] In general formula [D-16] - Formula [D-18], B is an oxygen atom or _{-N (Rd 6) - (Rd} 6 has the general formula [D-11], general formula [D- 14], general formula [D-1
5] has the same meaning as Rd ₆ in formula [D-19]. )
Represents

In the general formula [D-16]

[0034]

[Chemical 5]

Represents a single bond or a double bond. When m ₂ is 2, it is a single bond and when m ₂ is 1, it is a double bond.

[0036]

[Chemical 6]

Where T ₁ is

[0038]

[Chemical 7]

SR is the component that cleaves

[0040]

[Chemical 8]

After the formation of, by reaction with the oxidant of the color developing agent

[0042]

[Chemical 9]

[0043] The component that generates a, T ₂ is

[0044]

[Chemical 10]

A component which cleaves INHIBIT after the formation of, a group which becomes a development inhibitor after the cleavage of INHIBIT, and l ₁ and m ₃ are SR each representing 0 or 1
The component represented by, as long as it produces a compound 16 by the reaction with the oxidant of the color developing agent and further produces the chemical formula 17, for example, a coupler component and a coupling component which reacts with the oxidant of the color developing agent. A redox component that undergoes a redox reaction with an oxidized product of a color developing agent can be used.

As the coupler component, acylacetanilinos, 5-pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetanilides, 2 (5H) -imidazolones, 5- Isoxazolones, uracils,
Homophthalimides, oxazolones, 2,5-thiadiazolines-1,1-dioxides, triazolothiadiazines, indoles, yellow couplers, magenta couplers, cyan couplers, and various dyes It may be present or may be one which does not generate a dye.

[0047]

[Chemical 11]

Is preferably bonded to the active site of the A ₁ component of the general formula [DI].

When SR is a coupler component, SR is

[0050]

[Chemical 12]

Only after it is cleaved from

[0052]

[Chemical 13]

And

[0054]

[Chemical 14]

Is combined with For example, when the coupler component is phenols or naphthols, the oxygen atom of the hydroxyl group is, and when it is 5-pyrazolones, the oxygen atom of the 5-position hydroxyl group of the tautomer or the nitrogen atom of the 2-position is In the case of acetophenones and indanones,
The oxygen atom of the hydroxyl group of the tautomer is

[0056]

[Chemical 15]

Combined with

[0058]

[Chemical 16]

Is preferably attached to the active site of the coupler.

When SR is a redox component, examples thereof include hydroquinones, catechols, pyrogallols, aminophenols (for example, p-aminophenols and o-aminophenols), and naphthalenediols (for example, 1, 2-naphthalenediols, 1,4
-Naphthalene diols, 2,6-naphthalene diols), or aminonaphthols (for example, 1,2-aminonaphthols, 1,4-aminonaphthols, 2,6-
Aminonaphthols) and the like. When SR is a redox component, SR is

[0061]

[Chemical 17]

Cleavage from so that it functions as a redox component for the first time

[0063]

[Chemical 18]

And

[0065]

[Chemical 19]

Combined with

Examples of the groups represented by T ₁ and T ₂ include the groups represented by the above general formulas [D-11] to [D-19].

Examples of the group which serves as a development inhibitor after cleavage represented by INHIBIT include, for example, the above-mentioned general formula [D-
2] to groups represented by general formula [D-9].

Among the timing DIR compounds, INHIBIT ₁ in the general formula [D-I] is preferably the general formula [D-2], the general formula [D-3] and the general formula [D-6].
(In particular, when X in the general formula [D-6] is oxygen), or a group represented by the general formula [D-8] is preferable.

In the general formula [D-11] to the general formula [D-19] represented by TIME ₁ in the general formula [D-I], the general formula [D-12] to the general formula [D-14]. ] Is preferred.

In the general formula [DI], the coupler component represented by A ₁ includes a yellow image-forming dye coupler residue, a magenta image-forming dye coupler residue, a cyan image-forming dye coupler residue and a non-color-forming coupler. Residues. Of these, preferred are yellow image-forming dye coupler residues and cyan image-forming dye coupler residues.

Next, specific examples of the timing DIR compound represented by the general formula [DI] according to the present invention will be shown, but the present invention is not limited thereto.

[0073]

[Chemical 20]

[0074]

[Chemical 21]

[0075]

[Chemical formula 22]

[0076]

[Chemical formula 23]

[0077]

[Chemical formula 24]

[0078]

[Chemical 25]

[0079]

[Chemical formula 26]

[0080]

[Chemical 27]

[0081]

[Chemical 28]

[0082]

[Chemical 29]

[0083]

[Chemical 30]

[0084]

[Chemical 31]

Specific examples of the DIR compound that can be used in the present invention, including these, are described in US Pat. No. 4,234,678.
Issue 3,227,554, 3,617,291, 3,958,993,
4,149,886, 3,933,500, JP-A-57-56837,
51-13239, US Pat. Nos. 2,072,363 and 2,070,266, Research Disclosure (hereinafter abbreviated as RD) 19
December 1981 No. It is described in No. 21228.

Next, the above general formula [D-II] according to the present invention.
The compound represented by will be described.

In the general formula [D-II], A ₂ has the same meaning as A _{1 in} the general formula [D-I].

TIME ₂ is a TIME of the general formula [D-I].
Synonymous with ₁ , TIME ₂ may be present or may not be present at all (when n ₁ = 0) INH
IBIT ₂ is a group which serves as a development inhibitor and has the general formula [D
-IIa] and [D-IIb] are monocyclic triazole ring groups.

General formula [D-IIa] and general formula [D-II
In b], the alkylthio group represented by R ₁ or R ₂ preferably has 1 to 7 carbon atoms and may be substituted by one of the above-mentioned hydrolyzable groups.

The alkyl group represented by R ₂ or R ₃ preferably has 1 to 7 carbon atoms and may be substituted with a halogen atom, a cyano group or the like.

The heterocyclic group represented by R ₂ is, for example, a furyl group or the like.

The aryl group represented by R ₃ is, for example, a phenyl group or the like, which may be substituted with an alkyl group, a halogen atom or the like.

The groups --CO--OR ₃ , --O--CO--OR ₃ or --OC which can be hydrolyzed in aqueous alkali.
O-R ₃ and 2 that defines a spacing between the triazole ring group
The atoms of 4 can be carbon atoms and heteroatoms.

Typical examples of the triazole ring group represented by INHIBIT ₂ are shown below.

Exemplified Compound

[0096]

[Chemical 32]

[0097]

[Chemical 33]

[0098]

[Chemical 34]

[0099]

[Chemical 35]

Next, specific examples of the compound represented by the general formula [D-II] according to the present invention will be shown, but the present invention is not limited thereto.

[0101]

[Chemical 36]

[0102]

[Chemical 37]

[0103]

[Chemical 38]

[0104]

[Chemical Formula 39]

[0105]

[Chemical 40]

[0106]

[Chemical 41]

The DIR compound represented by the general formula [D-I] or the general formula [D-II] according to the present invention is preferably used in an amount of 0.0001 to 0.1 mol per mol of silver halide,
It is particularly preferable to use 0.001 to 0.05 mol.

The method of incorporating the DIR compound represented by the general formula [D-I] or the general formula [D-II] according to the present invention into a color photographic light-sensitive material is not particularly limited, but a conventional silver halide photographic light-sensitive material is used. All known methods for materials are available. That is, as shown in U.S. Pat.No. 2,322,027, a method of dissolving in a high boiling point solvent to disperse as fine oil droplets, as shown in U.S. Pat.No. 2,186,849, a dissolution-resistant group and a water-soluble group are added and dissolved. Dispersion Method, US Patent
No. 2,397,864, a method of incorporating it as a component of a polymer compound, a method of filling a latex polymer as shown in JP-A Nos. 51-59942 and 51-59943, or a machine using a colloid mill or the like. There is a method of pulverizing and dispersing.

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, by coupling with a colored coupler having a color correcting effect, a competing coupler and an oxidized product of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener and a hardener. Compounds that release photographically useful fragments such as film agents, antifoggants, 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 emulsion layers,
Dyes may be included which are bleached or bleached from the light-sensitive material during the development process. For the light-sensitive material, formalin scavenger, fluorescent whitening agent, matting agent, lubricant, image stabilizer, surfactant, color antifoggant, development accelerator,
Development retarders and bleaching accelerators can be added.

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

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.

[0116]

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 the following examples, the addition amount in the silver halide photographic light-sensitive material was 1 m ² unless otherwise specified.
The number of grams per unit is shown. The silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in the number of moles per mole of silver.

Example 1 Multilayer color photographic light-sensitive materials No. 1 to No. 10 were prepared by sequentially forming each layer having the following composition from the support side on a triacetyl cellulose film support.

First layer; antihalation 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 point solvent (Oil-) 1) 0.20 gelatin 1.5 second layer; intermediate layer (IL-1) UV absorber (UV-1) 0.01 high boiling solvent (Oil-1) 0.01 gelatin 1.5 third layer; low sensitivity red-sensitive emulsion layer (RL) iodine Silver bromide emulsion (Em-1) 0.8 Silver iodobromide emulsion (Em-2) 0.8 Sensitizing dye (SD-1) 2.5 × 10 ^-4 Sensitizing dye (SD-2) 2.5 × 10 ^-4 Sensitizing dye (SD-3) 0.5 × 10 ^-4 Cyan coupler (C-1) 1.0 Colored cyan coupler (CC-1) 0.05 DIR compound (shown in Table-1) 0.002 High boiling point solvent (Oil-1) 0.5 Gelatin 1.5 Fourth Layer: High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 2.0 Sensitized color Element (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD-2) 2.0 × 10 ^-4 Sensitizing dye (SD-3) 0.1 × 10 ^-4 Cyan coupler (C-1) 0.25 Cyan coupler (C- 2) 0.05 Colored cyan coupler (CC-1) 0.015 DIR compound (listed in Table-1) 0.05 High boiling point solvent (Oil-1) 0.2 Gelatin 1.5 Fifth layer; Intermediate layer (IL-2) Gelatin 0.5 Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 1.3 Sensitizing dye (SD-4) 5 × 10 ^-4 Sensitizing dye (SD-5) 1 × 10 ^-4 Magenta coupler (M -A) 0.50 Colored magenta coupler (CM-1) 0.01 DIR compound (listed in Table-1)
0.04 High boiling point solvent (Oil-2) 0.3 Gelatin 1.0 7th layer; High sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 1.3 Sensitizing dye (SD-6) 1.5 × 10 ^-4 Sensitizing dye (SD-7) 2.5 × 10 ^-4 Sensitizing dye (SD-8) 0.5 × 10 ^-4 Magenta coupler (MA) 0.15 Colored magenta coupler (CM-2) 0.05 DIR compound (described in Table-1) ) 0.01 High boiling point solvent (Oil-2) 0.2 Gelatin 1.0 8th layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Oil-3) 0.1 Gelatin 0.8 9th layer Layer: Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (SD-10) 7 × 10 ^-4 Yellow coupler (Y) -1) 0.5 Yellow coupler (Y-2) 0.1 DIR compound (listed in Table-1) 0.01 High boiling point (Oil-2) 0.3 Gelatin 1.0 10th layer; High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.4 Silver iodobromide emulsion (Em-1) 0.4 Sensitizing dye (SD-9) 1 × 10 ^-4 Sensitizing dye (SD-10) 3 × 10 ^-4 Yellow coupler (Y-1) 0.30 Yellow coupler (Y-2) 0.05 High boiling point solvent (Oil-2) 0.15 Gelatin 1.1 11th layer; 1st protective layer (PRO-1) Fine grain silver iodobromide emulsion (average grain size 0.08 μm, AgI content 2 mol%) 0.4 UV absorber (UV-1) 0.10 UV absorber (UV-2 ) 0.05 High boiling point solvent (Oil-1) 0.1 High boiling point 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 Alkali-soluble matting agent (average particle size 2 μm 0.05 Polymethylmethacrylate (average particle size 3 μm) 0.05 Sliding agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, each layer contains a coating aid Su-2, a dispersion aid Su-3, a hardener H-. 1 and H-2, stabilizer ST-
1, antifoggants AF-1 and AF-2 were added.

Em-1 Average grain size 0.46 µm Average silver iodide content 7.0 mol%, monodisperse (width of distribution 14%) surface low silver iodide (2 mol%) core / shell type emulsion Em -Average grain size 0.30 μm Average silver iodide content 2.0
Mol%, monodisperse (dispersion width 14%) surface silver bromide-containing core / shell type emulsion Em-3 average grain size 0.81 μm average silver iodide content 7.0
Core / shell emulsion containing mol% and monodisperse (14% of distribution) low surface silver iodide (1.0 mol%) Em-4 average grain size 0.95 μm average silver iodide content 8.0
Core / shell type emulsion containing mol% and surface low silver iodide (0.5 mol%) with monodispersity (width of distribution 14%)

[0121]

[Equation 1]

[0122]

[Chemical 42]

[0123]

[Chemical 43]

[0124]

[Chemical 44]

[0125]

[Chemical formula 45]

[0126]

[Chemical formula 46]

[0127]

[Chemical 47]

Each of the sample Nos. 1 to
After 10/100 second wedge exposure of 10 with white light,
The following development processing was performed.

Development processing step (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-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.05.

<Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Water is added to 1 liter and adjusted to pH 6.0.

<Fixer> Ammonium thiosulfate (50% aqueous solution) 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 with acetic acid.

<Stabilizing Solution> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

Sensitometric measurement was performed on the obtained treated sample to determine the green sensitivity. The sensitivity was calculated from the exposure amount required to give a density of minimum density + 0.1, and shown as a relative value with Sample 1 being 100.

The raw storability of samples 1 to 10 thus prepared was measured. The raw storability is that each sample is stored at a temperature of 45 ° C and a relative humidity of 80% for 12 days, and then exposed with green light through a step wedge for sensitometry together with each sample before storage. Development processing was performed and the green sensitivity S'was measured. The rate of change of the green sensitivity S of the sample before storage was calculated by the following formula. The sensitivity is minimum density +0.
It was calculated from the reciprocal of the exposure dose required to give a density of 1.

Rate of change = (| S−S ′ |) / S × 100 The IIE effect was determined by the following method. One sample was subjected to wedge exposure with white light, and the other sample was subjected to wedge exposure with blue light. For each sample, the gamma value was obtained from the characteristic curve of the yellow dye obtained by color development, and the value obtained by dividing the gamma by the blue light (γB) by the gamma by the white exposure (γW) was taken as the IIE effect.

The results are shown in Table 1.

[0138]

[Table 1]

As shown in Table 1, the comparative sample has a low sensitivity, a small IIE effect, and a large deterioration in raw storability.
On the other hand, Samples 2 to 10 of the present invention have high sensitivity and I
The IE effect is large and the raw storability is also good.

[0140]

According to the present invention, it is possible to provide a color photographic light-sensitive material having high sensitivity, excellent color reproducibility, and improved storability of raw samples.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. At least one of the blue-sensitive silver halide emulsion layers contains at least one compound represented by the following general formula [D-II], and the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. At least one layer of at least one compound represented by the following general formula [DI] is contained in the silver halide color photographic light-sensitive material. Formula [D-I] _{A 1 - (TIME 1) n} 1 -INHIBIT 1 wherein, A ₁ represents a coupler residue. TIME ₁ represents a timing group, is bonded to the coupling group A ₁ of the general formula [DI], and is cleaved from the coupler by the reaction with the oxidation product of the color developing agent, then sequentially cleaved, and finally To INH
Release IBIT ₁ with moderate control. n ₁ is 1 to 3, and when 2 and 3, each TIME ₁ may be the same or different. INHIBIT ₁ is a group which becomes a development inhibitor by the above release. ] Formula [D-II] _{A 2 - (TIME 2) n} 2 -INHIBIT 2 wherein, A ₂ represents a coupler residue. TIME ₂ represents a timing group, is bonded to the coupling group of A ₂ of the general formula [D-II], and is cleaved from the coupler by the reaction with the oxidized product of the color developing agent, and then sequentially cleaved to form the final compound. IN
HIBIT ₂ is released with moderate control. n ₂ is 0 or 1. INHIBIT ₂ is a group which becomes a development inhibitor by the above release and is a triazole ring group represented by the following general formula [D-IIa] or general formula [D-IIb]. [Chemical 1] R in the general formula [D-IIa] and general formula [D-IIb]
₁ is an alkylthio group, and R ₂ is H, an alkyl group, an alkylthio group, an aryl group or a heterocyclic group. At least one of the substituents R ₁ and R ₂ is 2 from the triazole ring.
A group capable of being hydrolyzed in aqueous alkali at intervals of 4 atoms
CO-OR ₃ , -O-CO-OR ₃ , or -CO-CO
Containing -R _3. R ₃ is an alkyl group, a cycloalkyl group, or an aryl group. ]