JPH0690464B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention relates to a color photographic light-sensitive material containing a novel compound capable of making a photographically useful group available during development processing.

(Prior Art) With respect to a color-reducing color photographic light-sensitive material, much research has been conducted so far for the purpose of improving sharpness, graininess, improving color reproducibility, or increasing sensitivity.

One such technique is a coupler that releases a photographically useful group. In addition to a coupler that releases a photographically useful group from the coupling position of a coupler, a coupler that releases a photographically useful group from a coupling position via a timing group has recently been disclosed. For example, U.S. Pat.Nos. 4,248,962 and 4,40
It is a coupler described in No. 9,323. On the other hand, in another attempt, an example of releasing from a coupler releasing a photographically useful group is disclosed in US Pat. No. 4,438,193.

These known couplers have a certain level of performance, but are still insufficient, and further improvement has been desired.

That is, in a recent high-sensitivity light-sensitive material, for example, a color negative film of ISO1600, the grain size is conspicuous because the size of silver halide is increased to increase the sensitivity, and improvement is desired. Moreover, since the film size of the disk camera, which is convenient for carrying, is small, it is necessary to further improve the sharpness of the image because of the large enlargement magnification at the time of printing.

(Object of the Invention) Accordingly, it is an object of the present invention to provide a color photographic light-sensitive material excellent in sharpness, graininess or color reproducibility or having high sensitivity.

(Constitution of the invention) The above-mentioned object is to release at least one kind of compound characterized by releasing a precursor of a compound capable of releasing a development inhibitor by being oxidized by a coupling reaction with an oxidant of a developing agent. And a silver halide color photographic light-sensitive material containing

Preferred couplers used in the present invention can be represented by the following general formula (I).

General formula (I) A-PRE-PUG In the formula, A is a PRE by undergoing a coupling reaction with an oxidized product of a developing agent.
-Represents a coupler residue that releases PUG, PRE represents a precursor of a compound which can be oxidized to release PUG after the bond with A is cleaved, and PUG represents a development inhibitor or its precursor.

The reaction process of the compound of the present invention can be described by the following reaction formula.

In the formula, A, PRE and PUG are the same as defined in the general formula (I).
The same meaning, T Represents an oxidized product of a developing agent, and RED
Represents a reducible organic atom dump and OX is its oxidation
Represents the body. However, in the above equation, the PUG generation process is mainly shown.
Since I have passed, for example, the coupling result generated from A
The body (eg pigment) is omitted.

The compounds of the present invention are reacted in at least four steps as described above.
To generate PUG. PUG is a development inhibitor precursor
Occasionally, a photographically useful group is formed through a one-step reaction.
To do. The present invention is characterized in that it goes through these series of reactions.
Be attached. Especially the process of generating OX-PUG from RED-PUG
Then T It is a secondary reaction with
Degree depends. Ie T When a large amount of
In the meantime, OX-PUG is released immediately. In contrast, T
Generation of OX-PUG when only a small amount is generated
The speed to do becomes slow. The principle of such secondary reactions and
The process of the reaction before and after that characterizes the effect of the present invention.
Evoke.

In the compound of the present invention, A, PRE and PUG can be selected in a wide range, and various sensitive materials (eg, color negative film, color reversal film, color positive film) are selected according to the selection.
Can be used by various known methods.
Generally, it can be used as a DIR coupler, a colored coupler, a competitive coupler or a development accelerating coupler by mixing with the main coupler, and it may also be used as the main coupler. As the layer to be used, any layer such as a high sensitivity layer or a low sensitivity layer can be selected according to the purpose.
Thus, the present invention includes a group of compounds which can be used for different purposes in different light-sensitive materials and by different ways of use. It is possible to select the property of the reaction product with the oxidized form of the developing agent by arbitrary selection of the coupling component A (for example, selection of dye to be formed, selection of uncolored product),
Features that the release rate of groups below PRE than A or the range of action of PUG can be easily adjusted by arbitrary selection of PRE, and that the type of photographic action can be selected according to the purpose by arbitrary selection of PUG This compound has

JP-A-57-138636 discloses an example of a coupler that releases an ED compound (reducing agent).

That is, the coupler of the application is represented by the following general formula.

General formula In the formula, COUP is a photographic coupler residue that reacts with an oxidized product of a color developing agent to form a dye image, ED is bonded to COUP at a coupling position of COUP, and is cleaved from the COUP to form an oxidized product of a reactive developing agent. It represents a group capable of undergoing a redox reaction.

This compound is merely for the purpose of reducing the oxidized product of the developing agent and is completely different from the present invention. The present invention is meaningful in releasing a photographically useful group, and controls the release depending on the concentration of an oxidized product of a developing agent,
At the same time, it has an excellent function of adjusting the diffusion range.

In general formula (I), A is specifically a yellow coupler residue (closed ketomethylene coupler, etc.), a magenta coupler residue (5-pyrazolone, pyrazolotriazole, pyrazoloimidazole, etc.), a cyan coupler residue (phenol, naphthol, etc.). ), And non-color-forming coupler residues (indanone, acetophenone, etc.).

As the yellow coupler mother nucleus, for example, U.S. Pat.
No. 506, No. 2,875,057, No. 3,408,194, JP-A-48-2943
No. 2, No. 48-66834, No. 54-13329, No. 50-87650 and the like, as a magenta coupler nucleus U.S. Patent Nos. 2,600,788, 3,062,653, 3,127,269, 3,4
19,391, 3,519,429, 3,888,680, JP-A-49-1
11631, 59-171956, 59-162548, etc., as cyan coupler mother nucleus U.S. Patent No. 2,474,29
No. 3, No. 2,801,171, No. 3,476,563, No. 4,009,035,
4,333,999, JP-A-50-112038, 50-117422,
55-32071, 53-109630, Research Disclosure (RD) 15741, JP-A-57-204545, and the like. Further, as a mother nucleus of a coupler that does not substantially form a dye, U.S. Patent Nos. 3,958,993 and 3,961,9
Examples include those described in No. 59.

Furthermore, the present invention is particularly effective when A in the general formula (I) is represented by the following general formulas (Cp-1) and (Cp-
2), (Cp-3), (Cp-4), (Cp-5), (Cp-
6), (Cp-7), (Cp-8), (Cp-9), (Cp-1)
0) or (Cp-11). These couplers are preferred because of their high coupling speed.

General formula (Cp-1) General formula (Cp-2) General formula (Cp-3) General formula (Cp-4) General formula (Cp-5) General formula (Cp-6) General formula (Cp-7) General formula (Cp-8) General formula (Cp-9) General formula (Cp-10) General formula (Cp-11) In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group. In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ ,
If R ₅₉ , R ₆₀ or R ₆₁ contains a diffusion resistant group, it is selected to have a total carbon number of 8 to 32, preferably 10 to 22, otherwise the total number of carbon atoms is 15 or less. Is preferred.

Next, R _{51 to} R ₆₁ l of the general formulas (Cp-1) to (Cp-11),
The m and p will be described.

In the formula, R ₅₁ represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group, and R ₅₂ and R ₅₃ each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R ₅₁ preferably has 1 carbon atom.
22 to 22 may be substituted or unsubstituted, linear or cyclic. Preferred substituents on the alkyl group are an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom and the like, which may themselves further have a substituent. Specific examples of aliphatic groups useful as R ₅₁ are: isopropyl group, isobutyl group, tert-butyl group, isoamyl group, tert-amyl group, 1,1-dimethylbutyl group, 1,1-dimethylhexyl group, 1,1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group,
2-p-tert-butylphenoxyisopropyl group, α-
Aminoisopropyl group, α- (diethylamino) isopropyl group, α- (succinimide) isopropyl group, α
Examples include-(phthalimido) isopropyl group and α- (benzenesulfonamide) isopropyl group.

When R ₅₁ , R ₅₂ or R ₅₃ represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups are alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, alkylureido groups. , An alkyl-substituted succinimide group or the like may be substituted, in which case the alkyl group may have an aromatic group such as phenylene interposed in the chain. The phenyl group may be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., and the aryl group of these substituents The moiety may be further substituted with one or more alkyl groups having 1 to 22 carbon atoms in total.

The phenyl group represented by R ₅₁ , R ₅₂ or R ₅₃ further includes an amino group substituted with a lower alkyl group having 1 to 6 carbon atoms, a droxy group, a carboxy group, a sulfo group,
It may be substituted with a nitro group, a cyano group, a thiocyano group or a halogen atom.

R ₅₁ , R ₅₂ or R ₅₃ may represent a substituent in which a funnel group is condensed with another ring, for example, a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group and the like. These substituents may themselves have a substituent.

When R ₅₁ represents an alkoxy group, the alkyl part thereof represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. It may be substituted with a halogen atom, an aryl group, an alkoxy group or the like.

When R ₅₁ , R _52, or R ₅₃ represents a heterocyclic group, the heterocyclic group may be a carbon atom of the carbonyl group of the acyl group in the alpha acylacetamide or an amide group of an acyl group in one of the carbon atoms forming the ring. Combines with the nitrogen atom. Examples of such heterocycles include thiophene, furan, pyran,
Examples are pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine and oxazine. These may further have a substituent on the ring.

In the general formula (Cp-3), R ₅₅ is a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (eg, methyl, isopropyl, tert-butyl, hexyl, dodecyl group, etc.), alkenyl group. (Eg, allyl group), cyclic alkyl group (eg, cyclopentyl group, cyclohexyl group, norbornyl group), aralkyl group (eg, benzyl, β-phenylethyl group, etc.), cyclic alkenyl group (eg, cyclopentenyl, cyclohexenyl group, etc.) Represents a halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, Carbamoyl group, acyla Mino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N
-Arylanilino group, N-alkylanilino group, N-
It may be substituted with an acylanilino group, a hydroxyl group, a mercapto group or the like.

Further, R ₅₅ may represent an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.). The aryl group may have one or more substituents, and examples of the substituent include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group and an alkoxy group. Group, aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl Group, alkylsulfonyl group,
Arylthio group, alkylthio group, alkylamino group,
It may have a dialkylamino group, an anilino group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino group, a hydroxyl group, and the like.

Further, R ₅₅ is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, a condensed heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group. , An oxazolyl group, an imidazolyl group, a naphthoxazolyl group, etc.), a heterocyclic group substituted by the substituents listed for the aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, An alkylcarbamoyl group,
It may represent an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

In the formula, R ₅₄ is a hydrogen atom and has 1 to 32 carbon atoms, preferably 1
22 straight-chain or branched alkyl, alkenyl,
Cyclic alkyl, aralkyl, cyclic alkenyl groups (these groups may have the substituents listed for R ₅₅ above), aryl groups and heterocyclic groups (these have the substituents listed for R ₅₅ above). ), Alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group, naphthoxycarbonyl group etc.), aralkyloxycarbonyl group (eg benzyl) Oxycarbonyl group, etc.), alkoxy group (eg methoxy group, ethoxy group,
Heptadecyloxy group etc.), aryloxy group (eg phenoxy group, tolyloxy group etc.), alkylthio group (eg ethylthio group, dodecylthio group etc.), arylthio group (eg phenylthio group, α-naphthylthio group etc.), carboxy group, acylamino Group (eg, acetylamino group, 3- [2,4-di-tert-amylphenoxy) acetamido] benzamide group, etc.), diacylamino group, N-alkylacylamino group (eg, N-methylpropionamide group), N- Arylacylamino group (for example, N-phenylacetamide group), ureido group (for example, ureido, N-arylureido, N-alkylureido group, etc.), urethane group, thiourethane group, arylamino group (for example, phenylamino, N- Methylanilino group, diphe Ruamino group, N-acetylanilino group, 2-chloro-5-tetradecanamidoanilino group, etc.), alkylamino group (for example, n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino group (for example, Piperidino group, pyrrolidino group etc.), heterocyclic amino group (eg 4-pyridylamino group, 2-benzoxazolylamino group etc.), alkylcarbonyl group (eg methylcarbonyl group etc.), arylcarbonyl group (eg phenylcarbonyl group) Etc.), sulfonamide group (eg alkylsulfonamide group, arylsulfonamide group etc.), carbamoyl group (eg ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N-phenylcarbamoyl etc.), sulfamoyl group (example N-
Alkylsulfamoyl, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N, N-diarylsulfamoyl group, etc.), cyano group, Represents either a hydroxy group or a sulfo group.

In the formula, R ₅₆ represents a hydrogen atom or a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, and these are It may have the substituents enumerated above for R ₅₅ .

In addition, R ₅₆ may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R ₅₅ .

In addition, R ₅₆ is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, Ureido group, urethane group,
Sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group, or hydroxyl It may represent a group.

R ₅₇ , R ₅₈ and R ₅₉ each represent a group used in a usual 4-equivalent phenol or α-naphthol coupler, and specifically, R ₅₇ is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group or an aliphatic carbon group. Hydrogen residue, N-arylureido group, acylamino group, -O-
R ₆₂ or -S-R ₆₂ (wherein R ₆₂ is an aliphatic hydrocarbon residue)
When two or more R _57's are present in the same molecule, the two or more R _57's may be different groups, and the aliphatic hydrocarbon residue has a substituent. including.

Further, when these substituents include an aryl group, the aryl group may have the substituents enumerated above for R ₅₅ .

Examples of R ₅₈ and R ₅₉ include an aliphatic hydrocarbon residue, a group selected from an aryl group and a heterocyclic residue, or one of these may be a hydrogen atom,
Also, those having a substituent in these groups are included. Also
R ₅₈ and R ₅₉ may together form a nitrogen-containing heterocyclic nucleus.

The hydrocarbon aliphatic residue may be saturated or unsaturated, and may be linear or branched.
Any of the annular ones may be used. And preferably an alkyl group (for example, each group of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.),
It is an alkenyl group (for example, each group such as allyl and octenyl). Typical examples of the aryl group include a phenyl group and a naphthyl group, and typical examples of the heterocyclic residue include pyridinyl, quinolyl, thienyl, piperidyl, and imidazolyl groups. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl,
Examples thereof include heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl and morpholino groups.

l represents an integer of 1 to 4, m represents an integer of 1 to 3, and p represents an integer of 1 to 5.

R ₆₀ is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and 1 to 32 carbon atoms, preferably 2 to 22 carbon atoms. Represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent, and examples of the substituent include an alkoxy group, an alkoxycarbonyl group, an acylamino group,
Examples thereof include an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsuccinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group or an aryl group.

R ₆₁ represents an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and 1 to 32 carbon atoms, preferably 1 to 22 Alkoxycarbonyl group or aryloxycarbonyl group with 1 carbon
To 32, preferably 1 to 22 alkylsulfonyl group, arylsulfonyl group, aryl group, 5-membered or 6-membered heterocyclic group (hetero atom is selected from nitrogen atom, oxygen atom and sulfur atom, for example, triazolyl group, imidazolyl group) Group, phthalimido group, succinimido group, furyl group,
A pyridyl group or a benzotriazolyl group), which may have the substituents described above for R ₆₀ .

Among the above coupler residues, as the yellow coupler residue, in the general formula (Cp-1), R ₅₁ is a t-butyl group or a substituted or unsubstituted aryl group, and R ₅₂ is a substituted or unsubstituted aryl group. Is preferred, and in the general formula (Cp-2), R ₅₂ and R ₅₃ are preferably a substituted or unsubstituted aryl group.

Preferred as the magenta coupler residue are those represented by the general formula (Cp
When R ₅₄ in -3) represents an acylamino group, a ureido group, and an arylamino group, and R ₅₅ represents a substituted aryl group, R ₅₄ in the general formula (Cp-4) represents an acylamino group, a ureido group, and an arylamino group, R _{54 When 56} represents a hydrogen atom, and the general formulas (Cp-5) and (Cp-5
In -6), R ₅₄ and R ₅₆ represent a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, or cyclic alkenyl group.

Preferred as the cyan coupler residue is a compound represented by the general formula (Cp-
R ₅₇ in 7) is an acylamino group or ureido group at the 2-position, an acylamino group or an alkyl group at the 5-position,
When the 6-position represents a hydrogen atom or a chlorine atom, R ₅₇ in the general formula (Cp-9) is a 5-position hydrogen atom, an acylamino group, a sulfonamide group or an alkoxycarbonyl group, and R ₅₈ is a hydrogen atom. Further, R ₅₉ represents a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, and a cyclic alkenyl group.

Preferred as the uncolored coupler residue are those represented by the general formula (Cp-
In the case where R ₅₇ represents an acylamino group, a sulfonamide group or a sulfamoyl group in 10), a compound represented by the general formula (Cp-1
In 1), R ₆₀ and R ₆₁ represent an alkoxycarbonyl group.

Further, at any part of R _{51 to} R ₆₁ , a multimer of bis form or more may be formed, and a polymer or non-polymer of a monomer having an ethylenically unsaturated group at any part of those groups. It may be a copolymer with a color forming monomer.

When the coupler residue of the present invention represents a polymer, a polymer having a repeating unit represented by the general formula (Cp-13), which is derived from a monomer coupler represented by the following general formula (Cp-12), or , At least one which does not have the ability to couple with oxidants of aromatic primary amine developing agents
It means a copolymer with one or more non-color-forming monomers containing one ethylene group. Where the monomer coupler is 2
One or more species may be polymerized at the same time.

General formula (Cp-12) General formula (Cp-13) In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and A ₁ represents -CONR'-, NR'CO.
NR '-, - NR'COO -, - COO -, - SO 2 -, - CO -, - N
_{RCO -, - SO 2 NR '} -, - NR'SO 2 -, - OCO -, - OCON
R '-, - NR'- or -O- and represents, A ₂ is -CONR'-
Or —COO—, R ′ represents a hydrogen atom, an aliphatic group, or an aryl group, and when there are two or more Rs in one molecule, they may be the same or different.

A ₃ represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group, and the alkylene group may be linear or branched.

(Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene,
Tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, arylene groups such as phenylene, naphthylene, etc.) Q represents R _{1 to} R in the general formulas (Cp-1) to (Cp-11). Any part of ₁₁ represents a group bonded to the general formula (Cp-12) or (Cp-13).

i, j and k represent 0 or 1.

Here, the substituent of the alkylene group, aralkylene group or arylene group represented by A ₃ is an aryl group (for example, a phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (for example, a methoxy group), an aryloxy group. (Eg phenoxy group), acyloxy group (eg acetoxy group), acylamino group (eg acetylamino group), sulfonamide group (eg methanesulfonamide group), sulfamoyl group (eg methylsulfamoyl group), halogen atom (eg fluorine group) Element, chlorine, bromine, etc.), a carboxy group, a carbamoyl group (eg, methylcarbamoyl group), an alkoxycarbonyl group (eg, methoxycarbonyl group, etc.), and a sulfonyl group (eg, methylsulfonyl group). When there are two or more substituents, they may be the same or different.

Next, acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid and their acrylic acids are derived as non-color-forming, ethylene-like monomers that do not couple with the oxidation product of the aromatic primary amine developing agent. Examples include esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, vinyl pyridines and the like. The non-color-forming ethylenically unsaturated monomers used here may be used in combination of two or more.

In the general formula (I), PRE is preferably represented by the following general formula. Here, the * mark represents the site that binds to A, and the ** mark represents the site that binds to PUG.

(P-1) _{(P-2) * -B 2} -RED - ** (P-3) In the formula, RED is specifically hydroquinone, catechol, pyrogallol, naphthohydroquinone, ortho- or para-position amino group-substituted phenol (wherein the amino group is a sulfonyl group, an aliphatic group, an aromatic group or a heterocyclic group). (Optionally substituted), bisphenols, or nitrogen-containing aromatics having a benzene ring moiety in the above compounds (eg, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, etc.)
The compound replaced by.

These REDs are mediated by the oxygen atom, which is the hydrogen atom removed from the hydroxyl group of the aromatic alcohol, and /
Alternatively, it is bonded to A, B ₁ or B ₂ via a nitrogen atom which is obtained by removing a hydrogen atom from the amino group of aromatic amines.

In the formula, B ₁ reacts with a nucleophile such as hydroxylamine or sulfite ion present in an alkali or a developing solution to produce RE.
Represents a group in which the bond with D is cleaved. Preferably, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxazolyl group, a hydrolyzable group such as a sulfonyl group, U.S. Pat.
A precursor group of the type utilizing the reverse Michael reaction described in 029, a precursor group of the type utilizing the generated anion as an intramolecular nucleophilic group after the ring opening reaction described in U.S. Pat. No. 3,674,478, No. 3,932,4
No. 80 or No. 3,993,661, the anion described in US Pat. No. 4,335,200 is a precursor group that undergoes electron transfer via a conjugated system to cause a cleavage reaction. Precursor group to wake up, or U.S. Pat.No. 4,363,865,
Precursor groups utilizing an imidomethyl group described in JP-A No. 4,410,618 are mentioned.

In the formula, B ₂ represents a group in which the bond with RED is first cleaved after the bond with A is cleaved. Preferable examples of B ₂ include (1) a group utilizing a cleavage reaction of hemiacetal, for example, US Pat. No. 4,146,396, Japanese Patent Application Nos. 59-106223 and 59-106.
A group described in Nos. 224 and 59-75475 and represented by the following general formula.

In the formula, * indicates the position of binding to A, and ** indicates RED
V represents an oxygen atom or a sulfur atom, R ₁ and R ₂ represent a hydrogen atom or a substituent, n represents 1 or 2, and when n is 2, two
R ₁ and R ₂ may be the same or different, and _two of arbitrary R ₁ and R ₂ may be connected to each other to form a cyclic structure.

(2) A group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction. For example, the timing groups described in US Pat. No. 4,248,962.

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system. For example, a group described in US Pat. No. 4,409,323 or a group represented by the following general formula (group described in British Patent 2,096,783A).

In the formula, * indicates the position of binding to A, and ** indicates RED
And R ₃ and R ₄ represent a hydrogen atom or a substituent.

The reaction for cleaving PUG from RED-PUG is described in, for example, British Patent No.
It is described in 1,097,064 and 1,058,606. In the compound of the present invention, the oxidant that oxidizes RED is considered to be an oxidant of the developing agent, but a part of it may be close to silver halide, causing a silver phenomenon, and as a result, a reaction in which RED is oxidized may be included. is there.

In the formula, the group represented by RED is preferably one represented by the following general formula. In the formula, * indicates the position for bonding to A or B ₂ , ** indicates the position for bonding to PUG, and when B ₁ bonds, D represents a hydroxyl group, and the oxygen atom except for the hydrogen atom is Connect through.

In the formula, D is a hydroxyl group, an aromatic sulfonamide group,
Represents an aliphatic sulfonamide group or a heterocyclic sulfonamide group, and W represents an aliphatic group, an aromatic group, a halogen atom, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. Group, sulfonyl group, sulfamoyl group, acylamino group, sulfonamide group, carbamoyl group, acyl group, nitroso group, acyloxy group, ureido group, imide group, nitro group, cyano group, heterocyclic group, heterocyclic thio group, hydroxyl group Represents a carboxyl group, an alkoxycarbonylamino group, a sulfo group, an amino group, an anilino group, a sulfinyl group, a sulfamoylamino group, a thioacyl group, a thioureido group or a heterocyclic amino group. n represents an integer of 0, 1 to 3, and n is 2
In the above case, W represents the same or different, and 2
When two W's are adjacent to each other, they are connected to each other by forming a divalent group to form a condensed ring to a benzene ring.
Such examples include benzonorbornenes, chromanes, indoles, benzothiophenes or indazoles. When the partial structure of W and D has an aliphatic group moiety, it has 1 to 22 carbon atoms, preferably 1 to 10 carbon atoms.
And is a linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group. When the partial structure of W and D contains an aromatic group, it has 6 to 10 carbon atoms and is preferably a substituted or unsubstituted phenyl group.

When PUG represents a precursor of a photographically useful group in the general formula (I), it is preferably a group that is cleaved from RED and then converted to a photographically useful group, or after cleaved from RED, it is further cleaved. Represents a group that releases a raised photographic group.

Examples of the group which is converted into a photographically useful group after being cleaved from RED include the development inhibitor precursor described in West German Published Patent (OLS) No. 3,307,506A. The development inhibitor precursor described in this patent is 5-anilino-1,2,3,4-thiatriazole. This compound itself does not have a development-inhibiting effect and reacts with an alkali during development to cause a rearrangement reaction.
-Development inhibitor action is exhibited only after the formation of -mercapto-1-phenyltetrazole.

Preferred examples of the group which, after being cleaved from RED, further undergoes a cleavage reaction to release a photographically useful group are the linking groups listed above for B ₂ .

The above development inhibitor also includes a case where it has the substituents enumerated for W above at substitutable positions.

The coupler of the present invention can be used in any layer such as a high speed layer or a medium speed layer, and can be used in a light sensitive silver halide emulsion layer or a layer adjacent thereto.

The addition amount of the compound of the present invention varies depending on the structure and use of the compound, but is preferably 1 × 10 ⁻⁶ to 1 mol, particularly preferably 1 ×, per 1 mol of silver present in the same layer or an adjacent layer.
It is from 10 ⁻³ to 5 × 10 ⁻¹ mol.

The compound of the present invention may be used alone in one layer, or may be used in combination with a known coupler. When used in combination with another color image-forming coupler, the ratio of the compound of the present invention to the other color image-forming coupler (the coupler of the present invention / the other color image-forming coupler) is from 0.1 / 99.9 to 90/10, preferably 5 / 95 ~ 5
It is 0/50.

Specific examples of the compound of the present invention will be given below, but the invention is not limited thereto.

Synthesis Example 1 Synthesis of Exemplified Compound (2) α-chloro-α-pivaloyl-2′-chloro-5′-
30 g of {4- (2,4-di-t-amylphenoxy) butanamide} acetanilide, 4-acetoxy-2-ethylcarbamoyl-3- (5-phenyltetrazolyl-1
22 g of -thio) phenol and 5,5 of triethylamine
g was added to 200 ml of acetonitrile and heated under reflux for 4 hours.
Ethyl acetate (500 ml) was added, and the mixture was washed with water, neutralized with dilute hydrochloric acid, and further washed with water until it became neutral. The oil layer was separated, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. From the residue, silica gel-filled column chromatography was performed to obtain 23 g of the desired compound (2).

Synthetic Example 2 Synthesis of Exemplified Compound (13) 20 g of 1,4-dihydroxy-2-naphthoic acid, 25.2 g of N-chloromethyl-N- (2,4-dihydroxyphenyl) methanesulfonamide and Zodium methoxide Side, 1
0.8 in N, N-dimethylformamide 200 ml under a nitrogen stream,
The reaction was carried out at room temperature for 2 hours. The reaction mixture was poured into dilute hydrochloric acid, and the precipitated crystals were collected by filtration. After drying the crystals and 2
− Tetradecyloxyaniline 30 g in acetonitrile 200
A solution of 20 g of N, N'-dicyclohexylcarbodiimide dissolved in 50 ml of acetonitrile was added dropwise thereto at room temperature. After reacting for 3 hours, the precipitated crystal was separated by filtration and the filtrate was concentrated. The residue was recrystallized from ethyl acetate and hexane to obtain 32 g of crystals. The crystals were added to 200 ml of acetonitrile. Separately, phenyltetrazolylsulfenyl chloride synthesized by a conventional method from 8.1 g of 5-mercaptophenyltetrazole and 6.5 g of sulfuryl chloride was added to the acetonitrile solution in three portions. After reacting for 1 hour, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate and hexane to obtain 19.8 g of the desired compound (13).

The silver halide photographic light-sensitive material used in the present invention may be a monochromatic color photographic light-sensitive material having one light-sensitive silver halide emulsion layer on a support, and a multi-layer color photographic light-sensitive material having at least two different spectral sensitivities on the support. It can also be applied to materials.

Multilayer color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. It is usual to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases.

In the same or other photographic emulsion layer or non-photosensitive layer of the photographic light-sensitive material produced by using the present invention, a color coupler, that is, aromatic 1 in color development processing, is used together with the compound represented by the above formula (I). A compound capable of forming a color by oxidative coupling with a primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative) may be used.

In the silver halide multilayer color photographic light-sensitive material of the present invention, yellow, magenta, and cyan color-forming couplers are usually used, but the couplers of the present invention can be used in all three colors, or if necessary. Thus, a part of the coupler of the present invention can be replaced with a conventionally known color coupler.

Useful color couplers are cyan, magenta and yellow color couplers, typical examples of which are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Diaclosure.
17643 (December 1978) Item VII-D and 18717 (December 1978 1
It is described in the patent cited in January).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. A two-equivalent color coupler in which a coupling active position is substituted with a leaving group, compared with a four-equivalent color coupler having a hydrogen atom, can reduce the amount of coated silver and obtain high sensitivity. A coupler having an appropriate diffusibility of a color forming dye, a colorless coupler, or a DIR coupler releasing a development inhibitor with a coupling reaction or a coupler releasing a development accelerator can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. Two equivalent yellow couplers include U.S. Pat.Nos. 3,408,194, 3,447,928, and 3,993,501.
No. 4 and No. 4,022,620, or an oxygen atom-releasing yellow coupler or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, RD18053 (197
April 9), British Patent No. 1,425,020, West German Application Publication No. 2,
Representative examples thereof include nitrogen atom-releasing yellow couplers described in No. 219,917, No. 2,261,361, No. 2,329,587 and No. 2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230.
(June 1984), and pyrazolopyrazoles. The imidazo compound described in European Patent 119,741 [1,2-
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.No. 4,052,212.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of phenol-based couplers include U.S. Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or higher at the meta position of the phenol nucleus described in US Pat. No. 3,772,002. Cyan coupler, U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 58-42671, and 2,5-diacylamino-substituted phenol-based couplers and U.S. Pat.No. 3,446,622.
Nos. 4,333,999, 4,451,559 and 4,42
No. 7,767, and the like, phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the like.

In order to correct the unnecessary absorption in the short wavelength region which the dyes formed from the magenta and cyan couplers have, it is preferable to use a colored coupler together with the color photosensitive material for photographing. Yellow colored magenta couplers described in U.S. Pat.No. 4,163,670 and JP-B-57-39413 or U.S. Pat.Nos. 4,004,929, 4,138,258 and British Patent 1,
Typical examples are the magenta colored cyan couplers described in JP-A-146368.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such blur couplers are described in U.S. Patent No. 4,366,237 and U.S. Patent No. 2,125,570.
No. 96,5 for a specific example of a magenta coupler.
No. 70 and West German Publication No. 3,234,533 have yellow,
Specific examples of magenta or cyan couplers are described.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

These couplers may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, it may be a colored coupler having a color correction effect, or a coupler releasing a development inhibitor upon development (so-called DIR coupler).

In addition to the DIR coupler, a non-color-forming DIR coupling compound which has a colorless coupling-reactive product and releases a development inhibitor may be contained. In addition to the DIR coupler, the photosensitive material may contain a compound that releases a development inhibitor upon development.

The above-mentioned various couplers may be used in combination of two or more kinds in the same photographic layer in order to satisfy the properties required for the light-sensitive material, or the same compound may be introduced in two or more different layers. You can also

In order to introduce the coupler of the present invention and the coupler which can be used together in the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2,322,027 is used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphonate, triphenyl phosphonate, tricresyl phosphonate, dioctyl butyl phosphonate), citric acid ester (eg acetyl) Tributyl citrate), benzoic acid esters (eg octyl benzoate), alkylamides (eg diethyllaurylamide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate) Or an organic solvent having a boiling point of about 30 to 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxy. After being dissolved in ethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Further, the dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin may be either lime-treated or acid-treated. See Arthur Weiss for details on how to make gelatin.
By The Macromolecular Chemistry of Gelati
n), (Academic Press), 196
Issued for 4 years).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide containing 15 mol% or less of silver iodide.
Particularly preferred is silver iodobromide containing 2 to 12 mol% of silver iodide.

The average grain size of silver halide grains in a photographic emulsion (the grain diameter in the case of spherical grains or grains close to spheres, the edge length in the case of cubic grains, and the average based on the projected area) is used. Although not particularly limited, it is preferably 3 μm or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystal bodies such as cubes and octahedra, and spherical,
Those having an irregular crystal body such as a plate shape, or a composite form of these crystal forms may be used. It may consist of a mixture of particles of different crystal forms.

It is also possible to use an emulsion in which ultra-thin tabular silver halide grains having a grain diameter 5 times or more the thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and outside. Further, it may be a particle in which a latent image is mainly formed on the surface or a particle in which a latent image is mainly formed inside the particle.

The photographic emulsion used in the present invention is P. glackid (P.
Glafkides), "Chimie et Physique Photographique"
(Published by Paul Montel, 1966),
VLZelikman, et al.,
"Making and Coating Photographi
c Emulsion ”(The Focal Press
Press) company publication, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a model for reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Good.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
Can also be used, that is, a so-called controlled double jet method can be used.

According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt and the like may coexist.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H.Fieser
Ed., “Die Grundlagender Photographischen Prozess,” by Die Grundlagender Photographischen Prozess.
e mit Silber Halogeniden) ”(Akademische Verlagegesel
lschaft), 1968), pp. 675-734.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, first tin salt, Reduction sensitization of amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds; precious metal compounds (eg gold complex salts, Pt, Ir,
A noble metal sensitizing method using a periodic salt group VIII metal complex salt such as Pd) or the like can be used alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc. Many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amide and the like can be added.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in smoothness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium salt. Compound, urethane derivative,
It may contain a urea derivative, an imidazole derivative, 3-pyrazolidones and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, vinyl ester (for example, vinyl acetate), acrytanitrile, olefin, styrene, etc., alone or in combination, or Acrylic acid, methacrylic acid,
A polymer having a monomer component of a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, and styrene sulfonic acid can be used.

The photographic emulsions used in this invention may be spectrally sensitive to methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon group is fused to these nuclei; and these Nucleus of fused aromatic hydrocarbon ring, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benz Imidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

With a sensitizing dye, a dye that does not itself have a spectral sensitivity effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may be included in the emulsion. For example,
Amino still compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat.Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,743,510), It may contain a cadmium salt, an azaindene compound or the like.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts (chromium vanillate, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urine sugar), methyloldimethylhydantoin, etc.), dioxane derivatives (2,3- Dihydroxydioxane, etc., active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy) -S-triazine and the like), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid and the like), etc. can be used alone or in combination.

In the light-sensitive material produced by using the present invention, when the hydrophilic colloid layer contains a dye or an ultraviolet absorber, they may be mordanted with a cationic polymer or the like.

The light-sensitive material produced by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color antifoggant.

The light-sensitive material produced by using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group (for example, those described in U.S. Pat.No. 3,533,794), a 4-thiazolidone compound (for example, those described in U.S. Pat. Kaisho 46
No. 2784), a cinnamic acid ester compound (for example, those described in U.S. Pat.Nos. 3,705,805 and 3,707,375), a butadiene compound (for example, those described in U.S. Pat. No. 4,045,229), or a benzoxazole compound ( For example, those described in US Pat. No. 3,700,455) can be used. UV absorbing couplers (eg α-
A naphthol-based cyan dye-forming coupler) or a UV-absorbing polymer may be used. These UV absorbers may be mordanted in a specific layer.

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, mellowanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more kinds. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenolic acids, p-oxyphenol derivatives and bisphenols.

Photographic processing of layers consisting of photographic emulsions made using the present invention include, for example, Research Disclosure 176, Nos. 28-3.
Any known method and known processing solution as described on page 0 can be applied. The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfoamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

In addition, FA Mason, “Photographic Processing Chemistry (Phot
Graphical Processing Chemistry) "(Focal Press, 1966), pages 226-229.
U.S. Patents 2,193,015 and 2,592,364, JP-A-48-64933
You may use those described in No.

Color developers also include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, silver bromide,
A phenomenon inhibitor such as iodide and an organic antifoggant or an antifoggant can be contained. If necessary, a water softener, a preservative such as hydroxylamine,
Organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid chelating agents, antioxidants It may also contain agents.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. Examples of bleaching agents include iron (III),
Cobalt (III), chromium (VI). Compounds of polyvalent metals such as copper (II), peracids, quinones, nitroso compounds and the like are used.

For example, ferricyanide, dichromate, iron (III)
Or an organic complex salt of cobalt (III) such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2
-Aminopolycarboxylic acids such as propanoltetraacetic acid or complex salts of organic salts such as citric acid, tartaric acid and malic acid; persulfates, permanganates and nitrosphenol can be used. The potassium uriferricyanide, sodium iron (III) ethylenediaminetetraacetate, and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

As the fixer, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Here, after the fixing step or the bleach-fixing step, washing with water,
Although it is common practice to carry out a treatment step such as stabilization, only a water washing step is carried out, and conversely, a substantial water washing step is not provided and only a stabilizing treatment step is carried out (Japanese Patent Laid-Open No. 57-8).
A simple treatment method such as Japanese Patent No. 543) can also be used.

The washing water used in the washing step may contain a known transfer agent, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides / antifungal agents that prevent the growth of various bacteria and algae, hardeners such as magnesium salts and ammonium salts, drying load, unevenness It is possible to use a surfactant or the like for preventing the above. Or LE West
st), “Water Quality Criteria (Wate
r Quality Criteria) ”Photographic Science and Engineering (Phol.Sci.and En
g.), Vol. 9 No. 6 Page 344 to 359 (1965) and the like can also be used.

In addition, the washing step may be performed using two or more tanks if necessary, and the washing water may be saved as multi-step countercurrent washing (for example, 2 to 9 steps).

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), and the like can be used. If necessary, a fluorescent whitening agent, a chelating agent, a bactericidal agent, an antifungal agent, a hardener, a surfactant and the like can be used in the stabilizing solution.

In addition, the stabilizing step may be performed using two or more tanks if necessary, and multi-stage countercurrent stabilization (for example, 2 to 9 steps) is performed to save the stabilizing solution, and the washing step may be omitted. You can also

(Examples) Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 A multi-layer color light-sensitive material sample comprising each layer having the following composition was prepared on a polyethylene terephthalate film support.

1st layer: Anti-halation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone 3rd layer: 1st red emulsion layer Iodour Silver halide emulsion (silver iodide; 5 mol%) ... Silver coating amount 1.6 g / m ² Sensitizing dye I ... 4.5 × 10 ^-4 mol sensitizing dye II per 1 mol of silver ..1.5 mol.times.10.sup.- ⁴ mol of coupler EX-1 per mol of silver 0.03 mol per mol of silver Coupler EX-3.0.003 mol per mol of silver Fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol%) ... Silver coating amount 1.4 g / m ² Sensitizing dye I ... 3 × 10 ^-4 mol Sensitizing dye II per 1 mol of silver ···· 1 mol of silver 1 × 10 ⁻⁴ mol Coupler EX-1 · 0.002 mol of silver 1 mol Coupler EX-2 · 0.02 mol of silver 1 mol Coupler EX-3 · silver 1 mol Against 0.0016 mol 5th layer; intermediate layer Same as 2nd layer 6th layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol%) ... Silver coating amount 1.8 g / m ² sensitizing dye III ・ ・ ・ ・ 5 × 10 ^-4 moles to 1 mole of silver Sensitizing dye IV ・ ・ ・ ・ 2 × 10 ^-4 moles to 1 mole of silver Coupler EX-4 ・ 0.05 moles to 1 mole of silver Coupler EX-5 / 0.008 mol per 1 mol of silver Coupler EX-9 / 0.0015 mol per 1 mol of silver 7th layer: second green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 8 mol%)・ ・ ・ ・ Silver coating amount 1.3g / m ² Sensitizing dye III ・ ・ ・ ・ ・ ・ 3 × 10 ^-4 mol Sensitizing dye IV ・ ・ ・ ・ ・ ・ 1.2 × 10 ⁻ 1 mol silver ⁴ mol Coupler EX-7. 0.017 mol per mol of silver Coupler EX-6. 0.003 mol per mol of silver 8th layer; yellow filter layer Yellow colloidal silver and 2,5-di-t in aqueous gelatin solution. -Emulsion dispersion of octyl hydroquinone Gelatin layer ninth layer comprising bets; to .... silver coverage 0.7 g / m ² Coupler EX-8 · 1 mol of silver; first blue-sensitive emulsion layer silver iodobromide emulsion (6 mol% silver iodide) 0.25 mol Coupler EX-9. 0.015 mol per 1 mol of silver 10th layer; second blue-sensitive emulsion layer Silver iodobromide (silver iodide; 6 mol%) ... Silver coating amount 0.6 g / m ² coupler EX-8, 0.06 mol per mol of silver 11th layer; 1st protective layer Silver iodobromide (silver iodide 1 mol%, average particle size 0.07 μ) ...
Silver coating amount 0.5 g / m ² Gelatin layer containing emulsified dispersion of UV absorber UV-1 12th layer; 2nd protective layer A gelatin layer containing polymethylmethanoacrylate particles (diameter about 1.5 μm) was coated.

In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each layer. Sample 10 was prepared as described above.
I set it to 1.

Preparation of Samples 102 to 110 The coupler EX-9 of the low green-sensitive emulsion layer of Sample 101 is shown in Table-1.
Sample 101 was prepared in the same manner except that it was changed as described above.

The samples 101 to 110 were subjected to a wet exposure with white light and were subjected to the processing described later, and almost the same sensitivity and gradation were obtained. The sharpness of the green-sensitive layer of these samples was evaluated using a conventional MTF value.

The structural formulas of the compounds used are as follows.

Compound used to make the sample Development processing was carried out at 38 ° C. according to the following processing steps.

Color development 2 minutes 45 seconds Bleach 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step is as follows. It was

Color developer Diethylenetriamine pentaacetic acid 1.0g 1-Hydroxyethylidene-1, 2.0g 1-Diphosphonic acid Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hi 4.5g Droxyethylamino) -2-methylaniline sulphate Add water 1.0l pH10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric iron 100.0g Ammonium salt Ethylenediaminetetraacetic acid dinatto 10.0g Lithium Ammonium chlorobromide 150.0g Ammonium nitrate 10.0g Add water 1.0l pH6.0 Fixer Ethylenediaminetetraacetic acid dinat 1.0g Lithium salt Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution 175.0ml (70%) Sodium bisulfite 4.6g Add water 1.0l pH6.6 Stabilizer Formalin (40%) 2.0ml Polyoxyethylene-p-mono 0.3g Nonylphenyl Ether were measured MTF values (average polymerization degree ≒ 10) Water to make present 1mm per 4 for 1.0l obtained samples and forty green-sensitive layer. The results are shown in Table-1.

From Table 1, it can be seen that the MTF value of the coupler using the coupler of the present invention is significantly higher than that of the ordinary DIR coupler.

Claims (1)

[Claims] 1. A halogen containing at least one compound characterized by releasing a precursor of a compound capable of releasing a development inhibitor by being oxidized by a coupling reaction with an oxidant of a developing agent. Silver halide color photographic light-sensitive material.