JPH06230529A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and color reproduction performance and further storage stability of a raw stock by incorporating a specified DIR compound in a blue-sensitive silver halide emulsion layer and a specified color- nondeveloping compound in a green-sensitive silver halide emulsion layer. CONSTITUTION:The silver halide color photographic sensitive material has on a support, photographic constituent layers comprising the blue-, green-, and red-sensitive silver halide emulsion layers, and at least one of the blue-sensitive emulsion layers contains the DIR compound represented by formula I or the like, and at least one of the green-sensitive emulsion layers contains the color- nonphotosensitive compound represented by formula II or the like. In formulae I and II, Cp is a coupler residue capable of coupling with the oxidation product of a color developing agent; Time is a timing group combined with the coupling site of the coupler; DI is a group to be a development after being released: k is 1 or 2: and each of R21 and R22, is H, alkyl, or the like.

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 which is excellent in color reproducibility and sharpness and is excellent in storability 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 which is excellent in color reproducibility, sharpness, and storage stability of raw samples. As a means for improving the sharpness, a DIR compound which reacts with an oxidized product of a color developing agent to release a development inhibitor is known. For example, US Pat. Nos. 3,227,554 and 3,701,783.
No. 3,632,345, JP-A-49-7763.
The mercapto-type DIR compound described in JP-A No. 5 and the like has a strong inhibitory effect in the layer, and it is possible to make the image finer particles, improve the sharpness and control the gradation, but the inhibitory effect to the adjacent layer. The so-called IIE effect was small and the color reproducibility was unsatisfactory.

[0003]

[Patent Document 1] US Pat.
148,062, JP-A-49-122355, 5
The DIR compound in which the inhibitory group described in JP-A-2-82424 is an azole type, for example, a benztriazole type, and JP-A-5-187
The DIR compound in which a hydrophilic group is substituted for the mercapto-based inhibitory group described in JP-A No. 5-135835 has a large diffusibility of the inhibitory group in gelatin or silver halide, and has an edge effect, IIE as compared with the mercapto-based compound described above. Although it is possible to further increase the effect, it is necessary to add a large amount in order to obtain a sufficient edge effect and IIE effect because the development inhibitory property of the suppressing group is small. In particular, D
When an IR compound is added to the blue-sensitive layer, the inhibitor released from the DIR compound diffuses into the developing solution, so that a very large amount of the DIR compound is required, and the DIR compound added to the emulsion is stored over time. However, there is a drawback in that the inhibitor generated therein desensitizes the layer as well as other layers.

An object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in sharpness and color reproducibility and is excellent in storability of raw samples.

[0005]

The objects of the present invention are achieved by the following silver halide color photographic light-sensitive materials. In 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, said blue-sensitive silver halide DIR represented by the following general formula [I] or general formula [II] in at least one of the emulsion layers
At least one compound containing at least one compound is added to at least one of the green-sensitive silver halide emulsion layers represented by the following general formula [A-
1] or at least one kind of the non-color-forming compound represented by [A-2], a silver halide color photographic light-sensitive material.

General formula [I] Cp- (Time) k-DI In the formula, Cp represents a coupler residue capable of undergoing a coupling reaction with an oxidized product of a color developing agent, and Time is bonded at the coupling position of Cp. Represents a timing group, DI represents a group that is cleaved to become a development inhibitor, and k represents an integer of 1 to 2.

[0007]

[Chemical 3]

In the formula, R ″ represents an alkyl group, a heterocyclic group or an aryl group. DI represents a group which is cleaved to become a development inhibitor.

General formula [A-1] R ₂₁ —NHSO ₂ —R _{22 In the} formula, R ₂₁ and R ₂₂ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or an aryl group. , A heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, or -N
It represents the (R ₂₃₎ R _24. Here, R ₂₃ and R ₂₄ each represent a hydrogen atom, an alkyl group or an aryl group.

[0010]

[Chemical 4]

In the formula, R ₃₁ represents an alkyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an arylsulfonylamino group or an alkylsulfonylamino group, an arylthio group, an alkylthio group, and R ₃₂ can be substituted on the benzene ring. Represents a group, m ₃₁ is 0
Represents an integer of 4;

The DIR compound represented by the above general formula [I] according to the present invention will be described in detail below.

The coupler residue represented by Cp includes a residue which produces a yellow, magenta or cyan dye and a residue which produces a substantially colorless product.

Of the coupler residues represented by Cp, typical yellow coupler residues are those disclosed in US Pat. Nos. 2,298,443, 2,407,210 and 2,875,057. No. 3,048,194,
No. 3,265,506, No. 3,447,928, and the like, and “Farbkuplerine Ritteratwer Verzicht Agfa Mittilinging (Band II)” (Farbkuplepleine Lite).
raturuversiecht AgfaMite
lung (BandII)) 112 to 126 (1961) and the like. Among these, acylacetanilides such as benzoylacetanilides and pivaloylacetanilides are preferable.

Typical examples of the magenta coupler residue are US Pat. Nos. 2,369,489 and 2,34.
No. 3,703, No. 2,311,182, No. 2,6
No. 00,788, No. 2,908,573, No. 3,
062,653, 3,152,896, 3,519,429, 3,725,067, 4,540,654 and the like, JP-A-59- 16
2548, and the aforementioned Agfa Mitell.
ung (Band II) pp. 126 to 156 (19
61) and the like. Of these, pyrazolone or pyrazoloazole (eg, pyrazoloimidazole, pyrazolotriazole, etc.) is preferable.

Typical examples of cyan coupler residues are US Pat. Nos. 2,367,531 and 2,42.
No. 3,730, No. 2,474,293, No. 2,7
No. 72,162, No. 2,395,826, No. 3,
No. 002,836, No. 3,034,892, No. 3,041,236, No. 4,666,999 and the like and the above-mentioned Agfa Mitellung (B.
and II) pp. 156 to 175 (1961). Of these, phenols or naphthols are preferable.

Representative coupler residues that form substantially colorless products are described, for example, in GB 861,
138, U.S. Pat. Nos. 3,632,345 and 3,3.
No. 928,041, No. 3,958,993 and No. 3,961,959. Of these, cyclic carbonyl compounds are preferred.

A typical timing group represented by TIME is the intramolecular nucleophilic substitution reaction disclosed in, for example, US Pat. No. 4,248,962 and JP-A-57-56837. Those releasing a photographically useful group, JP-A-56-114946 and JP-A-57-15423.
Examples thereof include those which release a photographically useful group by an electron transfer reaction along the conjugated chain disclosed in No. 4 and the like.

In addition, JP-A Nos. 57-188035, 58-98728, 59-206834 and 60.
-7429, 60-214358, 50-22
No. 5844, No. 60-229030, No. 60-233.
No. 649, No. 60-237446, No. 60-2374
The timing group disclosed in each publication such as No. 47 is also included.

As the yellow coupler residue represented by Cp in the general formula [I], those represented by the following general formulas [IIa] and [III] are preferable.

[0021]

[Chemical 5]

The above general formula [IIa] and general formula [II
I], R ₁ and R ₂ represent, for example, an alkyl, cycloalkyl, aryl, heterocycle or halogen atom, and the alkyl, cycloalkyl, aryl and heterocycle are bonded via an oxygen atom, a nitrogen atom or a sulfur atom. You may. Further, the alkyl, cycloalkyl, aryl and heterocycle may be bonded via the bonding groups listed below.

That is, acylamino, carbamoyl, sulfonamide, sulfamoyl, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido,
The thioureido, thioamido, sulfone, sulfonyloxy and the like, and the alkyl, cycloalkyl, aryl and heterocycle may further have a substituent described below.

That is, a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxy, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamide, Heterocycle, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxy, imide,
Acyl etc.

When there are two or more R ₁ and R ₂ respectively, they may be the same or different.

The magenta coupler residue represented by Cp in the general formula [I] is represented by the following general formula [IV],
Those represented by [V], [VI] and [VII] are preferable.

[0027]

[Chemical 6]

[0028] R ₁ of said R ₁ in the general formula [IV] - [VII], R ₂ is the general formula [IIa], [III], R
Synonymous with ₂ .

The cyan coupler residue represented by Cp in the general formula [I] is represented by the following general formula [VIII],
Those represented by [IX] and [X] are preferable.

[0030]

[Chemical 7]

[0031] R ₁ of said R ₁ in the general formula [VIII] - [X], R ₂ is the general formula [IIa], [III], R
Synonymous with ₂ .

As the coupler residue forming a substantially colorless product represented by Cp in the general formula [I], those represented by the general formulas [XI] to [XIV] are preferable.

[0033]

[Chemical 8]

In the formula, R ₃ is, 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 is an oxygen atom or
It represents an N-R _4. R ₄ represents an alkyl group, an aryl group, a hydroxy group, an alkoxy group or a sulfonyl group. Z
Is a 5- to 7-membered carbocycle (for example, indanone, cyclopentanone, cyclohexanone, etc.) or a heterocycle (for example, piperidone, pyrrolidone, hydrocarbostyril, etc.)
Represents a group of non-metal atoms necessary for forming.

[0035]

[Chemical 9]

[0036] In the formula, R ₃ and X have the same meanings as R ₃ and X in the general formula [XI], R ₅ is an alkyl group, an aryl group, a heterocyclic group, a cyano group, hydroxy group, alkoxy group, aryloxy Represents a group, a heterocyclic oxy group, an alkylamino group, a dialkylamino group, or an anilino group.

[0037]

[Chemical 10]

In the formula, R ₆ and R ₇ 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

[0039]

[Chemical 11]

Represents A 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.

[0041]

[Chemical 12]

In the formula, R ₈ is an alkyl group, an aryl group, an anilino group, an alkylamino group or an alkoxy group, and
Represents an oxygen atom, a sulfur atom or a nitrogen atom.

TIME useful in the present invention includes, but is not limited to, those represented by the following general formulas "XV", [XVI] and [XVII].

[0044]

[Chemical 13]

In the formula, X ₁ represents an atomic group necessary for completing a benzene ring or a naphthalene ring which may be a substituent. Y represents -O-, -S-, -N (R ₁₁ )-, is bonded to the coupling position of the coupler residue represented by Cp in the general formula [I], and R ₉ , R ₁₀ and R ₁₁ represents a hydrogen atom, an alkyl group or an aryl group. Also, −
The C (R ₉ ) (R ₁₀ )-group is substituted in the ortho or para position relative to Y and is attached to the sulfur atom of the development inhibitor group.

[0046]

[Chemical 14]

In the formula, Y, R ₉ and R ₁₀ are each represented by the general formula [X
V] has the same meaning as R ₉ and R ₁₀ . R ₁₂ is, for example, a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group or a heterocyclic residue, and R ₁₃
Represents a hydrogen atom, alkyl group, aryl group, heterocyclic residue, alkoxy group, amino group, acid amide group, sulfonamide group, carboxy group, alkoxycarbonyl group, carbamoyl group, cyano.

The timing group is represented by the general formula [X
In the same manner as V], Y at the coupling position of the coupler residue represented by Cp in the general formula [I] is -C (R ₉ ).
(R ₁₀₎ - is attached to a sulfur atom of the development inhibitor group with a group.

Next, an example of the timing group for releasing the development inhibitor group by the intramolecular nucleophilic substitution reaction is shown by the general formula [XVII].

[0050] In the general formula [XVII] -Nu-X ₂ -E- wherein, Nu is an electron-rich oxygen nucleophile having a sulfur or nitrogen atom, with Cp in the general formula [I] It is attached to the coupling position of the coupler residue represented.
E is an electrophilic group having a carbonyl group having insufficient electrons, a thiocarbonyl group, a phosphinyl group or a thiophosphinyl group, and is bonded to the sulfur atom of the development inhibitor group.

X ₂ sterically relates Nu and E, and after Nu is released from the coupler residue represented by Cp in the general formula [I], formation of a 3-membered ring to a 7-membered ring. Is a linking group capable of breaking the intramolecular nucleophilic reaction accompanied by and thereby releasing the development inhibitor.

K is preferably 1, and among TIME, preferred is the general formula [XV].

In the general formula [I], DI represents a group which becomes a development inhibitor when cleaved, and preferred development inhibitors include, for example, 5-mercaptotetrazole compounds (eg 1-phenyl-5-mercaptotetrazole, 1-
(4-hydroxyphenyl) -5-mercaptotetrazole, 1- (2-methoxycarbonylphenyl) -5-
Mercaptotetrazole, 1-ethyl-5-mercaptotetrazole and 1-propyloxycarbonylmethyl-5-mercaptotetrazole), benzotriazole compounds (eg 5- (or 6-) nitrobenzotriazole, 5- (or 6-) phenoxy) Carbonylbenzotriazole), 1,3,4-thiadiazole-based compound (for example, 5-methyl-2-mercapto-1,
3,4-thiadiazole, 5- (2-methoxycarbonylethylthio) -2-mercapto-1,3,4-thiadiazole), 1,3,4-oxadiazole compound (for example, 5-methyl-2-mercapto) -1,3,4-oxadiazole, 5-propoxycarbonyl-2-mercapto-1,3,4-oxadiazole), benzothiazole-based compound (e.g. 2-mercaptobenzothiazole), benzimidazole-based compound (e.g. 2-mercaptobenzimidazole), benzoxazole-based compounds (for example, 2-mercaptobenzoxazole), 1,
2,4-triazole compounds (for example, 3- (2-furyl) -5-hexylthio-1,2,4-triazole), 1,2,3-triazole compounds (for example, 4-
Hexyloxycarbonylmethylthio-1,2,3-triazole). The preferred DI is
It is a group that forms a 1,3,4-oxadiazole-based compound.

The development inhibitor is preferably a compound having a substituent containing a bond (for example, an ester bond, a urethane bond, a sulfonic acid ester bond and a carbonic acid ester bond) capable of causing a cleavage reaction during development processing.

The typical examples of the compounds represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0056]

[Chemical 15]

[0057]

[Chemical 16]

[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]

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

Examples of the alkyl group represented by R ″ include groups such as methyl, ethyl, butyl, hexyl, dodecyl and octadecyl.

Examples of the heterocyclic group represented by R ″ include groups such as thiazole, benzothiazole, thienyl and pyridyl.

Examples of the aryl group represented by R ″ include groups such as phenyl and naphthyl.

DI represents a group similar to DI in the general formula [I], preferably a benzotriazole compound,
Examples include 1,2,4-triazole compounds and 1,2,3-triazole compounds.

The representative examples of the compound represented by the general formula [II] of the present invention are shown below, but the present invention is not limited thereto.

[0072]

[Chemical 25]

[0073]

[Chemical formula 26]

[0074]

[Chemical 27]

[0075]

[Chemical 28]

[0076]

[Chemical 29]

Next, a compound represented by the general formula [A-1] will be described. In the general formula [A-1] R ₂₁ —NHSO ₂ —R ₂₂ , R ₂₁ and R ₂₂ are each a hydrogen atom or an alkyl group. Group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, or -N
(R ₂₃ ) represents R ₂₄ . Here, R ₂₃ and R ₂₄ each represent a hydrogen atom, an alkyl group or an aryl group. R ₂₃ and R ₂₄ may be the same or different.

The alkyl group represented by R ₂₁ and R ₂₂ has a carbon number of 1 to 32, an alkenyl group, and the alkynyl group has a carbon number of 2 to 32, a cycloalkyl group,
Examples of the cycloalkenyl group include those having 3 to 12 carbon atoms. The alkyl group, alkenyl group and alkynyl group may be linear or branched. Further, these groups also include those having a substituent.

The aryl group represented by R ₂₁ and R ₂₂ is preferably a phenyl group, and the group includes those having a substituent.

The heterocyclic group represented by R ₂₁ and R ₂₂ is preferably a 5- to 7-membered heterocyclic group, which may be condensed, and these groups include those having a substituent.

The alkoxy group represented by R ₂₁ and R ₂₂ includes those having a substituent, and examples thereof include a 2-ethoxyethoxy group, a pentadecyloxy group, a 2-dodecyloxyethoxy group and a phenethyloxyethoxy group. To be

The aryloxy group is preferably a phenyloxy group, and the aryl nucleus may be substituted, and examples thereof include a phenoxy group, a pt-butylphenoxy group and an m-pentadecylphenoxy group.

Further, the heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3,4,5,6-tetrahydro. Examples thereof include a pyranyl-2-oxy group and a 1-phenyltetrazole-5-oxy group.

Among the general formulas [A-1] of the present invention, particularly preferred are the compounds represented by the following general formula [A-3].

General formula [A-3] R ₂₅ —NHSO ₂ —R _{26 In the} formula, R ₂₅ and R ₂₆ are each an alkyl group or an aryl group, and these groups include those which are substituted. More preferably, at least one of R ₂₅ and R ₂₆ is an aryl group. Most preferably, both R ₂₅ and R ₂₆ are aryl groups, and particularly preferably phenyl groups.
Here, when R ₂₅ is a phenyl group, it is particularly preferable that the Hammett's σp value of the substituent at the para position of the sulfonamide group is −0.4 or more.

The alkyl group and aryl group represented by R ₂₅ or R ₂₆ are the same as those of R ₂₁ or R in the general formula [A-1].
It is synonymous with the alkyl group and aryl group represented by ₂₂ .

Further, the compound represented by the general formula [A-1] of the present invention may form a dimer or more multimer in R ₂₁ or R ₂₂ , and R ₂₁ and R ₂₂ are bonded to each other. To form a 5- or 6-membered ring.

The total number of carbon atoms of the non-color forming compound represented by the general formula [A-1] of the present invention is preferably 8 or more, particularly preferably 12 or more.

The typical examples of the compounds represented by formula (A-1) of the present invention are shown below.

[0090]

[Chemical 30]

[0091]

[Chemical 31]

[0092]

[Chemical 32]

[0093]

[Chemical 33]

[0094]

[Chemical 34]

The compound represented by the general formula [A-1] of the present invention can be synthesized by a conventionally known method such as the method described in Japanese Patent Application No. 61-20589.

Next, the compound represented by formula (A-2) will be described.

[0097]

[Chemical 35]

In the formula, R ₃₁ represents an alkyl group, an alkoxycarbonyl group, an arylsulfonyl group, an alkylsulfonyl group, an arylsulfonylamino group, an alkylsulfonylamino group, an arylthio group or an alkylthio group,
R ₃₂ represents a group capable of substituting on the benzene ring, and m ₃₁ represents 0 to 4
Represents the integer.

The alkyl group represented by R ₃₁ is preferably a linear or branched one having 1 to 32 carbon atoms, and these include those having a substituent. Examples of such alkyl groups include linear and branched butyl groups, hexyl groups, decyl groups,
Examples thereof include dodecyl group and octadecyl group.
Among the alkyl groups represented by R ₃₁ , those having 4 to 20 carbon atoms are particularly preferable, and those having 5 carbon atoms are more preferable.
~ 9.

The alkoxycarbonyl group represented by R ₃₁ preferably has 2 to 20 total carbon atoms. The alkyl moiety in these alkoxycarbonyl groups may be linear or branched, and these alkoxycarbonyl groups include those having a substituent. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, an undecyloxycarbonyl group, and an octadecyloxycarbonyl group. Among the alkoxycarbonyl groups represented by R ₃₁ , those having 2 to 14 carbon atoms in total are preferable, and those having 5 to 13 carbon atoms are more preferable.

Examples of the arylsulfonyl group represented by R ₃₁ include a benzenesulfonyl group and a naphthalenesulfonyl group, and these include those having a substituent. Specific examples of the arylsulfonyl group include p-toluenesulfonyl group, p-dodecylbenzenesulfonyl group, p-dodecyloxybenzenesulfonyl group, p-chlorobenzenesulfonyl group, p-octylbenzenesulfonyl group, 1-naphthalenesulfonyl group. , 4-dodecyloxynaphthalenesulfonyl group and the like.

The alkylsulfonyl group represented by R ₃₁ is preferably one having a linear or branched alkyl group having 1 to 32 carbon atoms, and these alkyl groups include those having a substituent. Examples of such an alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a linear and branched butylsulfonyl group, a dodecylsulfonyl group,
A hexadecyl sulfonyl group etc. can be mentioned.

Examples of the arylsulfonylamino group represented by R ₃₁ include a benzenesulfonylamino group and a naphthalenesulfonylamino group. These include those having a substituent. Specific examples of the arylsulfonylamino group include p-toluenesulfonylamino group and p-toluenesulfonylamino group.
-Dodecylbenzenesulfonylamino group, p-dodecyloxybenzenesulfonylamino group, p-chlorobenzenesulfonylamino group, p-octylbenzenesulfonylamino group, 1-naphthalenesulfonylamino group, 4-
A dodecyloxynaphthalene sulfonylamino group etc. can be mentioned.

The alkylsulfonylamino group represented by R ₃₁ is preferably one having a linear or branched alkyl group having 1 to 32 carbon atoms, and these alkyl groups include those having a substituent. Examples of such an alkylsulfonylamino group include a methylsulfonylamino group, an ethylsulfonylamino group, a linear and branched butylsulfonylamino group, a dodecylsulfonylamino group, and a hexadecylsulfonylamino group.

The aloolthio group represented by R ₃₁ is
Examples thereof include a phenylthio group, a naphthylthio group, a 3-t-butyl-4-hydroxy-5-methylphenyl group and a 4-hydroxyphenyl group.

The alkylthio group represented by R ₃₁ is
Those having a straight-chain or branched alkyl group having 1 to 32 carbon atoms are preferable, and these alkyl groups include those having a substituent. Specific examples of such an alkylthio group include a butylthio group, a hexylthio group, a dodecylthio group and an octylthio group.

The group capable of substituting on the benzene ring represented by R ₃₂ is not particularly limited, and examples thereof include halogen, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group. , Heterocyclic group, alkoxy group, aryloxy group, —N (R ₃₃ ) R ₃₄ (R
₃₃ and R ₃₄ each represent an alkyl group or an aryl group. ), Cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, nitro group, carboxyl group, sulfo group, alkylthio group, acylamino group, sulfonamide group, arylthio group, hydroxy group and the like. Chlorine is particularly preferable as the halogen.

Typical specific examples of the non-color forming compound represented by the general formula [A-2] of the present invention are shown below.

[0109]

[Chemical 36]

[0110]

[Chemical 37]

[0111]

[Chemical 38]

[0112]

[Chemical Formula 39]

[0113]

[Chemical 40]

[0114]

[Chemical 41]

These compounds can be easily synthesized by a conventionally known method. For example, US Pat. No. 2,8
It can be synthesized by the method described in the specification of No. 35,579.

The general formula [I] or the general formula [I
The DIR compound represented by the formula I] is usually 1 × 10 ⁻³ mol to 8 × 10 ⁻¹ mol, and preferably 1 × 10 ⁻³ mol, per silver halide.
It can be used in the range of 10 ⁻⁵ mol to ¹ × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻³ mol to 5 × 10 ⁻² m.
It is in the range of ol. .

The general formula [I] or the general formula [I
The DIR compound represented by I] can be used in combination with other types of DIR compounds.

The addition amount of the high boiling point solvent represented by the general formula [A-1] or the general formula [A-2] of the present invention is preferably 0.01 to 10 g, and more preferably 1 to 10 g of the magenta coupler. It is in the range of 0.1 to 3.0 g.

The high boiling point solvent represented by the general formula [A-1] or the general formula [A-2] of the present invention may be used in combination, or may be used in combination with another kind of high boiling point solvent. it can.

In order to incorporate the magenta coupler, a conventional method, for example, a high boiling point solvent represented by the general formula [A-1] or the general formula [A-2] of the present invention and butyl acetate, ethyl acetate or the like is used. Dissolve in a mixture of low boiling point solvents, either alone or in combination, and then mix with an aqueous gelatin solution containing a surfactant, and then emulsify and disperse using a high speed rotary mixer or colloid mill or ultrasonic disperser. After this, a method of directly adding to the emulsion can be adopted. Also, after setting the emulsified dispersion,
After shredding and washing with water, this may be added to the emulsion.

The magenta coupler may be separately dispersed in the high boiling point solvent and the above-mentioned dispersion method and added to the silver halide emulsion, but a method in which both compounds are dissolved at the same time, dispersed and added to the emulsion is preferable. .

The halogenated emulsion used in the light-sensitive material of the present invention may be any of the usual halogenated emulsions. 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 development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a color coupler, a competing coupler, and an oxidation product of a developing agent, which have an effect of color correction, by a coupling reaction. Compounds that release photographically useful fragments such as hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

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.

The present invention can be applied to color negative films, color papers, color reversal films and the like.

[0129]

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

Example 1 Multi-layer color photographic light-sensitive material samples Nos. 1 to 20 were prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

The addition amount in the multilayer color photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. or,
Silver halide and colloidal silver are shown in terms of silver. The sensitizing dye is shown by the number of moles per mole of silver.

First layer; antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling point solvent (Oil-1) 0 .20 High boiling point solvent (Oil-2) 0.20 Gelatin 1.6 Second layer; Intermediate layer (IL-1) Gelatin 1.3 Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.4 Silver iodobromide emulsion (Em-2) 0.3 Sensitizing dye (S-1) 3.2 × 10 ⁻⁴ Sensitizing dye (S-2) 3.2 × 10 ^{− 4} Sensitizing dye (S-3) 0.2 × 10 ⁻⁴ Cyan coupler (C-1) 0.50 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound ( DD-1) 0.01 High boiling point solvent (Oil-1) 0.55 Gelatin 1.0 Fourth layer; High Sensitive red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ Sensitizing dye (S-2) 1.6 × 10 ^{− 4} Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ Cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIR compound (DD-1) 0.02 High boiling point solvent (Oil-1) 0.25 Gelatin 1.0 Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.6 Silver iodobromide emulsion (Em-2) 0.2 Sensitizing dye (S-4) 6.7 × 10 ^-4 Sensitizing dye (S-5) 0.8 × 10 ^-4 Magenta coupler (M -A) 0.47 Colored magenta coupler (CM-1) 0.10 DIR compound (DD-3) 0.02 High boiling point solvent (described in Table 1) 0.70 Zera Down 1.0 7th layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S-6) 1.1 × 10 -4 Sensitizing dye (S -7) 2.0 × 10 ^-4 Sensitizing dye (S-8) 0.3 × 10 ^-4 Magenta coupler (MA) 0.20 Colored magenta coupler (CM-1) 0.04 DIR compound (DD -3) 0.01 High boiling point solvent (described in Table 1) 0.35 Gelatin 1.0 Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (SC-1) 0.12 High boiling point Solvent (Oil-2) 0.15 Gelatin 1.0 9th layer; Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0 .25 Sensitizing dye (S-9) 5.8 × 10 ^-4 Yellow coupler (Y-1) 0.60 Yellow coupler (Y-2) 0 .32 DIR compound (described in Table 1) 0.01 high boiling solvent (Oil-2) 0.18 gelatin 1.3 tenth layer; high-sensitivity blue-sensitive emulsion layer (BH) silver iodobromide emulsion (Em-4) ) 0.5 Sensitizing dye (S-10) 3.0 × 10 ^-4 Sensitizing dye (S-11) 1.2 × 10 ^-4 Yellow coupler (Y-1) 0.18 Yellow coupler (Y-2) ) 0.10 high boiling point solvent (Oil-2) 0.05 gelatin 1.0 11th layer; 1st protective layer (PRO-1) silver iodobromide emulsion (Em-5) 0.3 ultraviolet absorber (UV -1) 0.07 Ultraviolet absorber (UV-2) 0.1 Formalin scavenger (HS-1) 0.5 Formalin scavenger (HS-2) 0.2 High boiling point solvent (Oil-1) 0.07 High boiling point Solvent (Oil-3) 0.07 Gelatin 0.8 12th layer; 2nd protective layer PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 polymethylmethacrylate (average particle size 3 μm) 0.02 gelatin 0.5 In each layer, in addition to the above composition, a coating aid. SU-2, dispersion aid SU-1, hardener H-1, dyes AI-1, AI-
2 was added appropriately.

The emulsions used in the above samples are as follows. All of them are internal high iodine type monodisperse emulsions, and their distribution is 14%.

Em-1: Average silver iodide content 7.5 mol% Average particle size 0.55 μm Grain shape octahedron Em-2: Average silver iodide content 2.5 mol% Average particle size 0.36 μm Grains Shape octahedron Em-3: average silver iodide content 8.0 mol% average grain size 0.84 μm grain shape octahedron Em-4: average silver iodide content 8.5 mol% average grain size 1.02 μm grain Shape octahedron Em-5: average silver iodide content 2.0 mol% average grain size 0.08 μm

[0135]

[Chemical 42]

[0136]

[Chemical 43]

[0137]

[Chemical 44]

[0138]

[Chemical formula 45]

[0139]

[Chemical formula 46]

[0140]

[Chemical 47]

[0141]

[Chemical 48]

The obtained sample Nos. 1 to 20 were exposed to white light through a step wedge for sensitometry and then processed by the following processing steps.

[0143] The composition of the processing liquid used in each processing step 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 0.0 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. (PH = 10.05) <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 10.0 ml Water is added to make 1 liter. , PH with ammonia water =
Adjust to 6.0.

<Fixer> 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.

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

The raw storability of samples 1 to 20 thus prepared was measured. Raw preservation is the temperature of each sample is 45 ℃,
After storing at 70% relative humidity for 12 days, it was exposed to green light through a step wedge for sensitometry, and then the above-mentioned developing treatment was carried out to measure the green sensitivity S ′. The rate of change of the green sensitivity S of the sample before storage was calculated by the following formula. The sensitivity was calculated from the reciprocal of the exposure amount required to give a minimum density of 0.1.

Rate of change = (| S−S ′ |) / S × 100 Next, 1 to 20 are exposed to a sinusoidal wedge with white light for 1/100 second, and then the above-described developing process is performed to obtain green. The sharpness of the sensitive layer was sought. Sharpness is MTF of green dye image
(Modulation Transufer Function) value was evaluated, and the relative value of MTF at 20 lines / mm (Sample 1 was 100
And)).

The IIE effect was obtained by the following method.
One sample was subjected to wedge exposure with white light, and the other sample was subjected to wedge exposure with green light. For each sample, the gamma value was obtained from the characteristic curve of the magenta dye obtained by color development, and the value obtained by dividing gamma (γG) by green light by gamma (γw) by white exposure was defined as the IIE effect.

The results are shown in Table 1.

[0151]

[Table 1]

The comparative sample 1 using the comparative DIR compound and the comparative high boiling point solvent has a raw storability, an edge effect and IIE.
The effect is not enough. In addition, the comparative sample 2 using the DIR compound of the present invention and the comparative high boiling point solvent showed the edge effect, I
The IE effect is large to some extent, but the raw storage stability is also large. On the other hand, Samples 3 to 20 of the present invention had a large edge effect and IIE effect, and had good raw storability.

[0153]

According to the present invention, it is possible to provide a color photographic light-sensitive material having excellent color reproducibility, particularly edge effect and interlayer effect, 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 has the following general formula [I] or general formula [II]
And at least one of the green-sensitive silver halide emulsion layers contains at least one DIR compound represented by the following general formula [A-1] or [A-2] A silver halide color photographic light-sensitive material containing at least one kind. In the formula [I] Cp- (Time) k-DI, Cp represents a coupler residue capable of undergoing a coupling reaction with an oxidized product of a color developing agent, and Time represents a timing group bonded at the coupling position of Cp. , DI represents a group that is cleaved to become a development inhibitor, and k represents an integer of 1 to 2. [Chemical 1] In the formula, R ″ represents an alkyl group, a heterocyclic group or an aryl group. DI represents a group which is cleaved to become a development inhibitor. Formula [A-1] R ₂₁ —NHSO ₂ —R ₂₂ , R ₂₁ and R ₂₂ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, or —N.
It represents the (R ₂₃₎ R _24. Here, R ₂₃ and R ₂₄ each represent a hydrogen atom, an alkyl group or an aryl group. [Chemical 2] In the formula, R ₃₁ represents an alkyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an arylsulfonylamino group or an alkylsulfonylamino group, an arylthio group, an alkylthio group, and R ₃₂ represents a group capable of substituting on the benzene ring. M < ₃₁ > represents an integer of 0-4.