JPH0264539A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To make the color development of the subject material sufficient, and to improve the shelf-life of a picture, even when benzyl alcohol, etc., is not incorporated in a color developer, by incorporating a specified coupler in the photosensitive material. CONSTITUTION:The diequivalent coupler shown by the formula is incorporated in the emulsion layer or its adjacent layer of the photosensitive material. In the formula, A1 is a coupler residual group, X1 is -SO2NH- or -NHSO2- group, R1 is alkyl or phenyl, R2 is nitro or cyano, etc., R3 is a substituting group other then hydroxyl group, (l) is 1-5, (m) is 0-4. The yellow coupler residual group A1 is exemplified by a pivaloyl acetoanilide type or a malonic acid diester type residual group. The mazenta coupler residual group A1 is exemplified by a 5-oxo-2-pyrazoline type or a pyrazolotriazole type residual group, etc. The cyan coupler residual group A1 is a residual group contg. a phenol or a alpha-naphthol nucleus, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photographic coupler, particularly a color photographic light-sensitive material containing a novel two-equivalent coupler.

(Prior art) When a silver halide color photographic material is color developed, an oxidized aromatic primary amine color developing agent reacts with a coupler to produce indophenol, indoaniline,
It is known that indamine, azomethine, fenoxacin, quinone imine, phenazine and similar dyes are produced and color images are formed (e.g. T, H, J
The Theory of the
Photographic Process,”3r
d ed,, the Macmillan Co,,
New York, 1971゜pp382-396
), this method usually uses a subtractive color method for color reproduction, forming images in yellow, magenta, and cyan, which are complementary colors to silver halide emulsions that are selectively sensitive to blue, green, and red, respectively. agent is used. To form a yellow color image, for example, acylacetanilide, malondianilide, or dibenzoylmethane couplers are used, and to form a magenta color image, mainly pyrazolones, pyrazolobenzimidazole, cyanoacetophenone, pyrazolo are used. Triazole or indacylon couplers are used, and phenolic couplers such as phenols and naphthols are used to form cyan images.

Normally, color photographic materials are roughly divided into two types: an external method in which couplers are placed in a developing solution, and an internal method in which couplers are incorporated in each photosensitive layer of the material so as to maintain their independent functions. Ru. In the latter, the coupler forming the one-dye image is added to the silver halide emulsion. The coupler added to the emulsion must be non-diffusible (diffusible) in the emulsion binder matrix.

Heretofore, two-equivalent couplers have been known in which a group capable of leaving the coupler is substituted at the coupling position of the coupler after the coupler undergoes a coupling reaction with an oxidized developing agent. A 4-equivalent coupler requires a minimum of 4 equivalents of silver to produce 1 equivalent of dye, whereas a 2-equivalent coupler allows 2 equivalents of silver to produce 1 equivalent of dye. That is, when a 2-equivalent coupler is used, the amount of coated silver in the photosensitive material can be reduced, making it possible to reduce the cost and make the layer thinner.

Although known two-equivalent couplers have a certain degree of resistance, it has been desired to further improve their performance. In particular, it is unsatisfactory in terms of color development, which is a serious problem in high-temperature rapid processing that has recently become popular. In order to compensate for this insufficient color development, in some cases, an organic solvent such as benzyl alcohol is added to the developer as a color development promoter. However, these organic solvents for promoting color development have several drawbacks.

For example, in (1) the developing step, it is absorbed into the emulsion layer, so the amount in the developer decreases, resulting in a decrease in color development.

(2) It is carried into the bleach or bleach-fix solution, inhibiting desilvering and reducing dye density.

(3) Remains in the photosensitive material after processing and reduces color image fastness.

(4) It mixes into the treated wastewater and causes an increase in BOD and COD of the wastewater.

For these reasons, it has been highly desired to eliminate or reduce the amount of organic solvents used to promote color development.

From this viewpoint, techniques for improving the coloring properties of couplers have been proposed.

For example, US Pat. No. 4,401,752 proposes a group having a polarizable carbonyl group, sulfonyl group, or phosphinyl group in the ortho position of the oxygen atom of an aryloxy group. However, although these couplers have slightly improved color development compared to conventional couplers,
It's still not enough.

U.S. Patent No. 4,511,649 has the following general formula (A)
A coupler having a group represented by at the coupling position has been proposed.

General formula (A) (wherein, R1 and R2 represent substituents such as halogen atoms, alkyl groups, aryl groups, and aralkyl groups, Zl represents 10- or -S-, and Xl represents a divalent organic linking group. fL represents 0 or 1, n and m independently represent integers from 0 to 4,
n+m is an integer from 1 to 8, and when n or m is 2 or more, R1 and R2 may be the same or different.) This coupler is improved in terms of color development compared to conventional couplers. , it was still not sufficient, and further studies revealed that the storage stability of the obtained dye images was insufficient.

(Problems to be Solved by the Invention) A first object of the present invention is to provide a coupler suitable for a silver halide color photographic light-sensitive material having excellent color development properties. In particular, it is an object of the present invention to provide a color photographic material that has sufficient color development even when an organic solvent for promoting color development such as benzyl alcohol is removed from a color developer.

A second object of the present invention is to provide a novel silver halide color photographic light-sensitive material in which the dye images produced have excellent storage stability, that is, light fastness, heat resistance, and moisture resistance.

(Means for Solving the Problems) The present inventors developed a silver halide photographic emulsion layer imagewise exposed in the presence of a coupler represented by the following general formula (I) using an aromatic primary amine developer. It has been found that the above objects can be achieved by forming a dye image using a dye image.

General formula (I) (wherein (A1) represents a coupler residue from which one hydrogen atom at the coupling position has been removed, Xl represents a group represented by -502NH- or -NH802-, and R1 represents an alkyl group or represents a phenyl group, R2 represents a nitro group, cyano group, trifluoromethyl group, halogen atom, alkylsulfonyl group, arylsulfonyl group, or alkoxycarbonyl group, R3 represents a substitutable group other than a hydroxyl group, !; L represents an integer from 1 to 5, m represents 0.1.2.3 or 4.) General formula (
The compound represented by I) will be explained in detail below.

When (A1) in general formula (I) represents a yellow image forming coupler residue, examples thereof include pivaloylacetanilide type, benzoylacetanilide type,
Malon diester type, malon diamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type, benzothiazolylacetate type,
Benzoxacylylacetamide-type, benzoxacylylacetate-type, benzimidazolylacetamide-type or benzimidazolylacetate-type coupler residue derived from heterocycle-substituted acetamides or heterocycle-substituted acetates contained in U.S. Pat. No. 3,841,880 Coupler residue or U.S. Pat. No. 3,770,4
No. 46, British Patent No. 1,459,171, West German Patent (
OLS) No. 2,503,099, Japanese published patent 50
-139738 or Research Disclosure No. 15737, or a coupler residue derived from the acylacetamides described in US Patent No. 4,046,57.
Examples include the heterocyclic coupler residue described in No. 4.

When [A1] represents a magenta image-forming coupler residue, examples thereof include 5-oxo-2-pyrazoline type,
Pyrazolobenzimidazole type, pyrazolotriazole type, cyanoacetophenone type, pyrazoloimidazole type or OLS No. 3,121,955
Examples include N-heterocyclic acylacetamide type coupler residues described in No.

When (A1) represents a cyan image-forming coupler residue, mention may be made of a coupler residue having a phenol nucleus or an α-naphthol nucleus.

In addition to these, resorcinol, 3-aminophenol, and the like can be mentioned as coupler residues that form black or gray dyes by reaction with oxidized color developing agents.

In general formula (I), R1 represents an alkyl group or a phenyl group, and the alkyl group preferably has 1 to 2 carbon atoms.
0, the phenyl group preferably has 6 to 20 carbon atoms. Alkyl groups are unsubstituted alkyl groups (e.g. methyl, ethyl,
butyl) and substituted alkyl groups (e.g. methoxyethyl, methanesulfonylethyl, benzyl, phenethyl, 2
-chloroethyl). The phenyl group may be unsubstituted or substituted with the following substituents. For example, an alkyl group (
Examples include methyl, ethyl), halogen atoms (eg, chlorine atoms), and alkoxy groups (eg, methoxy).

In general formula (I), R2 is a nitro group, a cyano group, a trifluoromethyl group, a halogen atom (for example, a chlorine atom, a bromine atom), an alkylsulfonyl group (preferably a carbon number of 1
~20 1 such as methanesulfonyl, 2-butoxyethanesulfonyl), arylsulfonyl (preferably those having 6 to 20 carbon atoms, such as benzenesulfonyl,
(p-chlorobenzenesulfonyl, m-nitrobenzenesulfonyl), alkoxycarbonyl group (preferably one having 2 to 20 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl).

In general formula (I), R3 represents a substitutable group other than a hydroxyl group, such as an alkyl group (preferably one having 1 to 20 carbon atoms).

For example, methyl, ethyl, methoxymethyl), aryl group (preferably one with 6 to 20 carbon atoms, such as phenyl,
p-chlorophenyl), aralkyl group (preferably one with 7 to 20 carbon atoms, such as benzyl), alkoxy group (
Preferably those with a carbon number of 2 to 20, such as methoxy, ethoxy), acylamino groups (preferably 1 to 2 carbon atoms)
1 (e.g. acetamide), sulfonamide group (preferably one with 1 to 20 carbon atoms, e.g. methanesulfonamide, benzenesulfonamide), sulfamoyl group (preferably one with 0 to 20 carbon atoms, e.g. methylsulfamoyl) , carbamoyl group (preferably 0 to 0 carbon atoms)
20, e.g. ethylcarbamoyl), alkenyl group (preferably one having 2 to 20 carbon atoms, e.g. allyl)
can be mentioned.

In general formula (I), when m is 2 or more, R
2 and R3 may be the same or different.

A more preferred coupler in general formula (I) is general formula C
(A1) represented by I) has the following general formula (III),
(IV), (V), (Vi[), (
VII) , (■), (■)1, (X), (X[)
or when it is a coupler residue represented by (XI).

General formula (m) R7-C-CH-C-NH-R8 General formula (IV) II II R9-NH-C-CH-C-NH-R8 General formula (V) General formula 1) General formula (■) General formula (Vllll) General formula (X) General formula (X[) General formula (XII) R16-CH-R17 In the above formula, the free bond derived from the coupling position is the bonding position of the coupling-off group. represent.

In the above formula, R7, R8'R9'R10' R1
1. When R12, R13, R14, RIs, R16, or R17 contains a diffusion-resistant group, it means that the total number of carbon atoms is 8.
~32, preferably 10-22,
In other cases, the total number of carbon atoms is preferably 15 or less.

Next, the general formula (m) to (XlI) R7 to R17, x
, y and t will be explained.

In the formula, R7 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R8 and R9 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R7 preferably has 1 carbon number.
In ~22, preferred substituents to the alkyl group, which may be substituted or unsubstituted, chain or cyclic, are an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom, etc. It may further have a substituent. Specific examples of aliphatic groups useful as R7 are: isoprobyl groups,
Isobutyl group, tert-butyl group, isoamyl group, t
art-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-
Examples include (diethylamino)isopropyl group, α-(succinimide)isopropyl group, α-(phthalimido)isopropyl group, α-(benzenesulfonamido)isopropyl group, and the like.

When R7, R8 or R9 represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , alkyl may be substituted with a succinimit group, etc.; in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain; the phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, group, arylamide group, arylsulfamoyl group, arylsulfonamide group, arylureido group, etc., and the aryl group portion of these substituents further has one carbon number in total of 1 to 22. It may be substituted with any of the above alkyl groups.

The phenyl group represented by R7, R8 or R9 may further include an amine group, including one substituted with a lower alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group, a cyano group, a thiocyano group, or May be substituted with a halogen atom.

Also R7. R8 or R9 may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, etc. These substituents themselves It may further have a substituent.

When R7 represents an alkoxy group, the alkyl portion 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, and these are halogen It may be substituted with an atom, an aryl group, an alkoxy group, etc.

When R, R or R9 represents a heterocyclic group, the heterocyclic group is connected to the carbon atom of the carbonyl group of the acyl group or the nitrogen atom of the amide group in alpha-acylacetamide, respectively, through one of the carbon atoms forming the ring. Join. Such heterocycles include thiophene, furan, pyran, and role.

Examples include pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, oxazine, and the like. These may further have a substituent on the ring.

In general formula (V), RIG is a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl group, etc.), alkenyl group (e.g., allyl group), cyclic alkyl group (e.g. cyclopentyl group, cyclohexyl group).

norbornyl group, etc.), aralkyl group (e.g., benzyl, β-phenylethyl group, etc.), cyclic alkenyl group (e.g., cyclopentenyl, cyclohexethyl group, etc.), and these represent halogen atoms, nitro groups, cyano groups, aryl groups, Alkoxy group, aryloxy group, carboxyl group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino 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-acylanilino group, hydroxy group,
It may be substituted with a mercapto group.

R10 is an aryl group (e.g. phenyl group, α-
or β-naphthyl group). The aryl group may have one or more substituents, such as 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, Alkoxy 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, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxyl group , a mercapto group, etc. More preferred as R1□ is phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. This is because the coupler remaining in the film is less likely to change color due to light or heat. It is useful.

R10 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 heteroatom, a fused heterocyclic group, a pyridyl group, a quinolyl group,
furyl group, benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), heterocyclic group substituted with the substituents listed for the above aryl group, aliphatic or aromatic acyl group, alkylsulfonyl group, arylsulfonyl group may represent an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

In the formula, R1□ is a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (these groups are the same as those listed for R1 above). (which may have a substituent), an aryl group, and a heterocyclic group (these are the above R1
may have the substituents listed for □), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.)
, aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, heptadecyloxy group, etc.), aryloxy Group (
For example, phenoxy group, tolyloxy group, etc.), alkylthio group (for example, ethylthio group, dodecylthio group, etc.),
Arylthio groups (e.g. phenylthio group, α-naphthylthio group, etc.), carboxyl group, acylamino group (e.g. acetylamino group, 3-((2,4-di-tert-
(amylphenoxy)acetamide]benzamide group, etc.)
, diacylamino group, N-alkylacylamino group (for example, N-methylpropionamide group, etc.), N-arylacylamino group (for example, N-phenylacetamide group, etc.), ureido group (for example, ureido, N-arylureido group, etc.) , N-alkylureido group, etc.), urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-
acetylanilino group, 2-chloro-5-tetradecanamideanilino group, etc.), alkylamino group (e.g. n
-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino group (e.g. piperidino group,
pyrrolidino group, etc.), heterocyclic amino group (e.g., 4-pyridylamino group, 2-benzoxasilylamino group, etc.)
, alkylcarbonyl group (e.g. methylcarbonyl group), arylcarbonyl group (e.g. phenylcarbonyl group etc.), sulfonamide group (e.g. alkylsulfonamide group, arylsulfonamide group etc.), carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group etc.) group, N-methyl-phenylcarbamoyl, N-
phenylcarbamoyl, etc.), sulfamoyl groups (e.g. N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N-
(alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.), cyano group, hydroxyl group, mercapto group, halogen atom, and sulfo group.

In the formula, R1□ represents a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group, and these are the above-mentioned It may have the substituents listed for R11.

Further, R12 may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R1 above.

R1□ is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxyl 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, or an ureido group. 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
-It may represent an acylanilino group, a hydroxyl group or a mercapto group.

R13, R14 and R15 each represent a group used in a conventional 4-equivalent phenol or α-naphthol coupler, and specifically R13 is a hydrogen atom,
Halogen atom, alkoxycarbonylamino group, aliphatic hydrocarbon residue, N-arylureido group, acylamino group, -0-R,8 or -s -R18 (ta, dashi R1
8 is an aliphatic hydrocarbon residue), and 2 in the same molecule.
When two or more R13s are present, the two or more R13s may be different groups, and the aliphatic hydrocarbon residues include those having substituents.

Furthermore, when these substituents include an aryl group, the aryl group may have the substituents listed for R1□ above.

R and "15" can include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom,
These groups also include those having substituents. Further, R14 and R15 may jointly form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic.

and preferably an alkyl group (e.g. methyl, ethyl,
propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.), and alkenyl groups (for example, allyl, octenyl, etc.). Aryl groups include phenyl and naphthyl groups, and representative heterocyclic residues include pyridinyl, quinolyl, thienyl, piperidyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxyl, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, Aryloxy, arylthio, arylazo, acylamino,
Examples include carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, morpholino, and the like.

X represents an integer of 1 to 4, y represents an integer of 1 to 3, and t represents an integer of 1 to 5.

R16 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 1 ~22
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, an alkylsulfamoyl group, an alkylsulfonamide group, and an alkylsuccinimide group. group, halogen atom, nitro group, carboxyl group.

These include nitrile groups, alkyl groups, and aryl groups.

R1□ 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, or an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms; 1-22
an alkoxycarbonyl group or an aryloxycarbonyl group, having 1 to 32 carbon atoms. Preferably 1 to 22 alkanesulfonyl groups, arylsulfonyl groups, aryl groups, 5- or 6-membered heterocyclic groups (the hetero atoms are selected from nitrogen atoms, oxygen atoms, and sulfur atoms, such as triazolyl groups and imidazolyl groups) , a phthalimide group, a succinimide group, a furyl group, a pyridyl group, or a benzotriazolyl group), which may have the substituent described above for R16.

The most preferred couplers of the present invention are of the following general formula (■
It is indicated by

General formula (!I) In the formula (A2) represents the yellow coupler residue shown in the general formula (III) or (IV), R1, R, R,
X, , u and m have the same meanings as in general formula (I).

Specific examples of couplers used in the present invention are shown below, but the present invention is not limited thereto.

Specific examples of magenta couplers (M-1) (M-2) (M-3) Shi81'il?翫U (M-4) Specific example of cyan coupler (c-2) H (C-3) H (C-4) Synthesis example Synthesis of exemplified coupler (Y-2) Synthesis was performed by the following route.

Compound 2 63.4g, triethylamine 25g N,
Dissolved in 300 d of N-dimethylacetamide. 30~
A solution of 18.2 g of the compound Nino in 50 ml of acetonitrile was added dropwise while stirring at 40°C.

After reacting at 30-40°C for 3 hours, water soom[! and extracted with 400 d of ethyl acetate. 2% organic layer
It was washed twice with 300 d of an aqueous solution of sodium hydroxide.

After making it acidic with dilute hydrochloric acid, it was washed twice with water. The organic layer was dried over magnesium sulfate and then concentrated under reduced pressure to obtain a residue. This was subjected to silica gel chromatography to concentrate the part containing the target compound, and the exemplified compound (Y-
19.4g of 2) was obtained. The structure was confirmed by observing (M+H)''=923 using fast atom bombardment ionization mass spectrometry (FAB-MS) positive detection method.

The compound of general formula (I) according to the invention can be applied to a multilayer multicolor photographic material having at least three different spectral sensitivities on a support.
It can be applied mainly to improve sharpness, sensitivity, and color reproducibility. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. The compound of the present invention is used in the emulsion layer or a layer adjacent thereto. Further, the compound of the present invention can be used in any layer such as a high-sensitivity layer, a low-sensitivity layer, or a medium-sensitivity layer.

The amount of the compound of general formula (I) to be added varies depending on the structure of the compound, but is preferably lXl0-5 to 1.0 mol, particularly preferably lXl0-4 to 0.0 mol per mol of silver present in the same layer or an adjacent layer. It is 5 moles.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one blue-sensitive silver halide emulsion layer on a support. In general color photographic paper, these light-sensitive emulsion layers are coated on a support in the order listed above, but they may be coated in a different order. The subtractive color method is achieved by incorporating a silver halide emulsion sensitive to the wavelength range and a so-called color coupler that forms a color complementary to the light to which it is exposed - yellow for blue, magenta for green, and cyan for red. Color reproduction can be performed. however,
The coloring hues of the photosensitive layer and the coupler may not correspond as described above.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less, even if the halogen composition of the emulsion differs between grains. Although the halogen composition may be equal to 1, it is easy to make the properties of each grain uniform by using an emulsion having an equal halogen composition among the grains. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called homogeneous structure in which the composition is the same in all parts of the silver halide grains, and cores inside the silver halide grains (
Particles with a so-called layered structure in which the halogen composition differs between the core) and the surrounding shell [-layer or multiple layers], or particles with a non-layered portion with a different halogen composition inside or on the surface of one particle (particle surface) In this case, particles having a structure in which parts of different compositions are joined on the edges, corners, or surfaces of the particles can be appropriately selected and used. To obtain high sensitivity.

It is more advantageous to use one of the latter two types than grains with a uniform structure, and it is also preferable from the viewpoint of pressure resistance.When silver halide grains have the above-mentioned structure, it is preferable to use one of the latter two types rather than grains with a uniform structure. The boundary between the parts may be a clear boundary or may be a continuous structural change formed by forming a mixed crystal due to compositional differences.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Further, so-called high silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized layer is inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above.The halogen composition of the localized layer is The silver bromide content is preferably at least 10 mol %, more preferably more than 20 mol %, and these localized layers are within the two grains or on the edges, corners or surfaces of the grain surfaces. However, one preferred example is one in which part of the corner of the grain is epitaxially grown.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in high silver chloride emulsions with a kM silver content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution. In such cases, the silver chloride content is 98 mol% or more.
Emulsions of almost pure silver chloride, such as 100 mol %, are also preferably used.

Average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of the salt equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1 to 2 l.

In addition, the particle size distribution of these particles is preferably monodisperse with a coefficient of variation (standard deviation of particle size divided by average particle size) of 20% or less, preferably 15% or less. In this case, a wide latitude can be obtained. For this purpose, it is preferable to blend the above monodispersed emulsions in the same layer or to apply them in multiple layers.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Alternatively, it may be composed of a mixture of crystals having various crystal forms.

In the present invention, it is preferable that particles having the above-mentioned regular crystal form be contained in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P, Glafkide.
Chimie at Ph1sique Pho
tographique (Pau1Monte1, 1967), G. F. Duffin, Photographic Emulsion Ch
emistry (published by Focal Press, 19
1966), V. L., Zelikman et al.
Al, Making and Coating Ph.
otographic Emulsion (Focal
Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may include the one-sided mixing method, the simultaneous mixing method, and a combination thereof. May be used. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method)
You can also use As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies widely depending on the purpose, but is preferably 10 to 1 O@-2 mol relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. This is preferably carried out by adding an absorbing dye - a spectral sensitizing dye. Examples of the spectral sensitizing dye used in this case include those by F. M. Ilarmer, l.
1eterocyclic compounds-1y
anine dies and related co
mpounds (John Wiley & 5ons
[New York, London 1, 196
4) can be mentioned. Examples of specific compounds include the above-mentioned Japanese Patent Application Laid-Open No. 62-215272.
Those described in the upper right column of page 22 to page 38 of the specification of the publication are preferably used.

The silver halide emulsion used in the present invention is used to prevent fogging during the manufacturing process, storage, or photographic processing of light-sensitive materials.

Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. These are commonly called photographic stabilizers. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. It's okay.

Known photographic additives that can be used in the present invention include research and
It is stated in the disclosure.

The relevant entries are shown in the table below.

Additive type 1 Chemical sensitizer 2 Sensitivity increasing agent spectral sensitizer, supersensitizer brightener Antifogging agent and stabilizers light absorber.

Filter Dyes Ultraviolet Absorber Stain Inhibitor Dye Image Stabilizer Hardener Binder Plasticizer, Lubricant Coating Aid, Surfactant Static Inhibitor RD 17643 Page 23 Page 23-24 Page 24 Page 24-25 Page 25-26 Page 25 Pages right column 25 pages 26 pages 26 pages 27 pages 26-27 pages 27 pages RD 18716 648 pages right column Same as above page 648 right column ~ 649 right column 649 pages right column ~ 649 right column ~ 650 pages left column 650 pages left ~ Right column page 651 Left column Same as above Page 650 Right column Same as above Same as above In addition, in order to prevent the deterioration of photographic performance due to formaldehyde gas, it is described in U.S. Pat. It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure.
(RD) No. 17643, ■-C to G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4.401.752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425°020, British Patent No. 1,476.760, U.S. Patent No. 3,973,968, British Patent No. 4,314,
No. 023, No. 4,511,649, European Patent Ring No. 24
9.473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (1984) June), Japanese Patent Application Publication No. 1983
-33552, Research Disclosure No.
24230 (June 1984), JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patent Nos. 4,500,630 and 4,540,6
No. 54, No. 4,556,630, WO (PCT) 8
Particularly preferred are those described in No. 8104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052,212.
No. 4,146,396.

No. 4,228,233, No. 4,296,200, No. 2,369. ．． No. 929, same No. 2.801.17
No. 1, No. 2,772,162, No. 2,895,8
No. 26, No. 3,772,002, No. 3,758,
No. 308, No. 4,334.011, No. 4,327
, 173, West German Patent Publication No. 3,329,729, European Patent No. 121.365A, European Patent No. 249,453A, US Patent No. 3,446,622, German Patent No. 4.333.
No. 999, No. 4,753,871, No. 4.753
, No. 871, No. 4,451,559, No. 4,42
7.76'1, 4,690.889, 4,
Preferred are those described in No. 254,212, No. 4,296,199, JP-A-61-42658, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No. 17643.
Section ■-G, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, No. 4,138°258, British Patent No. 1,146,
The one described in No. 368 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat.
No. 4,576.910, British Patent No. 2,102
, No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
■-Patent listed in Section F, JP-A-57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and US Pat. No. 4,248,962.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound-emitting couplers or DIR coupler-emitting couplers, DIR coupler-emitting couplers described in JP-A-60-185950, JP-A-62-24252, etc. coupler, DIR coupler-releasing redox compound or DIR redox compound-releasing redox compound, coupler releasing a dye that recolors after separation as described in European Patent No. 173,302A, R,D
, No. 11449, No. 24241. Unexamined Japanese Patent Publication 1986-20
Examples thereof include bleach accelerator-releasing couplers described in US Pat.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above high boiling point organic solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate). , bis(2,4-di-t-amyl phenyl) isophthalate, bis(1,l-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, 2-di-2-ethylhexyl phenyl phosphate, etc.)
, benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,
4-di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives ( N,N-dibutyl-2-butoxy-5-t-octylaniline, etc.), hydrocarbons (
paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent,
Boiling point of about 30°C or higher, preferably 50°C or higher, about 160°C
An organic solvent having a temperature of 0.degree. C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right l181
Other types of high-boiling organic solvents that can be effectively used in the couplers of the present invention described in the upper right column of pages 144 to 144 include N,N-dialkylaniline derivatives. Among these, those in which an alkoxy group is bonded to the ortho position of the N,N-dialkylamino group are preferred, specifically, for example, N,N-di-n-butyl-2-n
-butoxy-5-tert-octylaniline.

This type of high boiling organic solvent is useful in preventing the formation of magentastin over time on the white background of color prints during processing, and also in preventing fog from development. The amount used is generally 10 mol% to 500 mol%, preferably 20 mol% to 300 mol%, per coupler.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203'716) in the presence or absence of the high-boiling organic solvents mentioned above, or water-insoluble and organic solvents. It can be dissolved in a soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic light-sensitive materials, and reflective supports can be used. It is more preferable to use

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support.8 For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide. Film, polycarbonate film, polystyrene film, vinyl chloride resin, etc.
These supports can be appropriately selected depending on the purpose of use.

The color photographic material according to the present invention includes the above-mentioned RD, N
o, 17643, pages 28-29, and same No. 187
16-651 left column to right column can be used for development processing.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or antifoggant such as benzimidazoles, benzothiazoles or mercapto compounds. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (l,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol (benzyl alcohol is preferably 2 ml or less per developer solution, and it is most preferable not to contain it), polyethylene glycol, quaternary ammonium salts, amines, etc. development accelerators, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, l-
An auxiliary developing agent such as phenyl-3-pyrazolidone, a viscosity imparting agent, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N, Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 3 times per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 m1.
You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact surface of the processing tank with the air. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment (bleaching treatment) or separately (bleaching treatment), or in order to speed up the processing, a method may be employed in which bleaching treatment is followed by bleaching treatment.

Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include compounds of polyvalent metals such as iron (■), cobalt (■), chromium (■), and copper (n), peracids,
Typical bleaching agents include ferricyanide; dichromate: organic complex salts of iron (m) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid. Acetic acid, methyliminodiacetic acid, 1,3
- Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. Can be done. Among these, aminopolycarboxylic acid iron (m) including ethylenediaminetetraacetic acid iron (m) complex salt
Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron (m) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (I[r) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. You can also do it.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059.988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95631, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
No. 53-28426, Research Disclosure No. 17129 (July 1978), etc. Compounds having a mercapto group or disulfide group:
Thiazolidine derivatives described in JP-A-50-140129; JP-A-45-8506, JP-A-52-20832
No. 53-32735, U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61: West German Patent No. 1,127
, 715, and the iodide salts described in JP-A-58-16235; West German Patent Nos. 966.410 and 2,748.43.
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compounds described in No. 8836: Other JP-A No. 4
No. 9-42434, No. 49-59644, No. 53-9
．． No. 4927, No. 54-35727, No. 55-265
Compounds of No. 06 and No. 58-163940: bromide ion, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Pat.
The compounds described in No. 1 are preferred.

Furthermore, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to light-sensitive materials. agents are particularly effective.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, especially ammonium thiosulfate or the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
our own of the 5ociety of
MotionPicture and Te1eviS
ion Engineers Volume 64, 9.248-2
53 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, "Chemistry of antibacterial and fungicidal agents" written by Hiroshi Hori, "Sterilization of microorganisms, sterilization, and antimagnetic technology" written by Hiroshi Hori, "Encyclopedia of antibacterial and antifungal agents" by Japan Antibacterial and Antifungal Science. It is also possible to use the fungicides described in .

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 25 to 45°C.
A range of 30 seconds to 5 minutes at ~40°C is selected.

The pH of the water washing step or stabilization step of the present invention is 4 to 10, preferably 5 to 8. Temperature depends on the use of photosensitive materials.
Although it can be set variously depending on the characteristics, etc., the zero time can be set arbitrarily, and is generally 15 to 45°C, preferably 20 to 40°C, but a shorter time is desirable from the viewpoint of reducing processing time. Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute
It is minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specific preferable replenishment amount is O.S to 50 times the amount brought in from the previous bath per unit area of the photosensitive material, preferably 3 to 4
It is 0 times. Or, the amount of blood per meter of the photosensitive material is 1i or less, preferably 500 or less.

Further, replenishment may be performed continuously or intermittently.

Furthermore, the photosensitive material of the present invention can be directly processed with a stabilizing solution instead of the above-mentioned washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Furthermore, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to flow the overflow of washing water reduced by a multistage countercurrent system into a bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid to reduce the amount of waste liquid.

The total process time of the desilvering process, water washing and stabilization process of the present invention is 2 minutes or less, preferably 30 seconds to 1 minute 30 seconds.

The total time here refers to the time from when the silver halide color photographic light-sensitive material comes into contact with the first bath in the desilvering process until it comes out of the last bath in the water washing or stabilization process. Air time for is included.

Here, "the sum of the processing times of desilvering treatment, water washing treatment, and stabilization treatment is 2 minutes or less" means the treatment performed before the desilvering treatment and drying process (more specifically, For example, the sum of the processing times such as (desilvering → water washing) ■desilvering → stabilization (desilvering → water washing → stabilization) is less than 2 minutes.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Ship base type compounds described in Research Disclosure No. 14850 and Research Disclosure No. 15159, Research Disclosure No. 13
Aldol compounds described in '924, U.S. Patent No. 3.71
Metal salt complex described in No. 9,492, JP-A-53-1356
Examples include urethane compounds described in No. 28.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
A treatment using cobalt intensification or hydrogen peroxide intensification as described in , 674.4'39 may also be carried out.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,826, JP-A No. 80-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Effects of the Invention) The silver halide color photographic material of the present invention has high sensitivity and excellent color development. Furthermore, the color image formed by this silver halide color photographic light-sensitive material has excellent heat resistance, moisture resistance, and light fastness.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 A photographic element was prepared consisting of layers of the composition described below on a paper support laminated on both sides with polyethylene.

Layer - Mix the coupler and di-n-butyl phthalate so that the weight ratio is 8=1, add ethyl acetate and dissolve by heating, then gelatin containing a surfactant (sodium dodecylbenzenesulfonate) An emulsified dispersion of a coupler was obtained by emulsifying and dispersing it in an aqueous solution, and a silver chlorobromide emulsion (80 mol% silver chloride) was mixed with a molar ratio of silver to coupler of 3.
．． A mixed solution was prepared at a ratio of 5:1.

Second layer: gelatin aqueous solution containing hardening agent (1,3-vinylsulfonyl-2-propanol) and surfactant (Tri
ton X-200) was prepared.

Coating samples 100 to 117 were produced by changing the couplers used in the first layer as shown in Table 1. The amount of coupler applied is for yellow coupler (Samples 101-1
10) is 1.211!101/go, for magenta coupler and cyan coupler (sample 111 to l 17) 0
, 7 mmol/rn'.

In addition, the following comparative couplers were used in the examples.

(A) Coupler Cσ described in JP-A No. 62-250446 (B) Coupler described in U.S. Pat. No. 4,401,752 (C) Coupler described in U.S. Pat. No. 4,511,649 (D) Couplers described in U.S. Pat. No. 4,511,649 (J Coupler described in U.S. Pat. No. 4,401,752 LJ2t, 4Mg1nl) After exposing each sample through an optical wedge, Development processing was performed using the following processing steps.

Processing process (33℃) Color development (A) or (B) Bleach and fixation for 3 minutes and 30 seconds
Rinse with water for 1 minute and 30 seconds
3 minutes drying 10 minutes Ingredients for each treatment step are as follows.

Benzyl Alcohol 15d Diethylene Glycol 5ml Potassium Carbonate
25g sodium chloride
0.1g sodium bromide 0.5g anhydrous sodium sulfite 2g hydroxylamine sulfate 2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate group 4g Add water to 14
12. Then, add NaOH to adjust the pH to 10.3.

The composition was the same except that benzyl alcohol was removed from the upper color developer (A).

1 Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Anhydrous sodium sulfite
2.7g EDTA ferric ammonium salt 65
g Add water to make one sentence and adjust the pH to 6.8.

The color density of each developed sample was measured. Table 1 shows the gamma and D wax of each sample.

In addition, in order to examine the storage stability of the dye images of Samples 101 to 110, a dye image storage stability test was conducted as described in (a) and (b) below.

(a) Photobleaching property (b) Dark fading property 100@C 70'C No humidification 80% RH 10 days 20 days The dye image storage stability is the density after the test (D ) expressed as a percentage (%). The results are shown in Table 2.

As can be seen from Table 2 and Table 1, samples of the present invention lOO~107,
111-112, 114-116 are comparative samples 108-1
10.It exhibits sufficient color development compared to 113 and 117, and has the characteristic that there is almost no decrease in density (Dmax) and gamma (γ) in color developer (B) without benzyl alcohol. . Furthermore, as can be seen from Table 2, the samples of the present invention are excellent in both photobleaching and implicit fading.

Example 2 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of exemplary coupler (Y-1) and color image stabilizer (
Cpd-1) 4.4g with ethyl acetate 27, 21Tlit
Add and dissolve 7.7mi of solvent (Solv-1),
This solution was emulsified and dispersed in 185 d of a 10% aqueous gelatin solution containing 8 ml of 1O% sodium dodecylbenzenesulfonate. On the other hand, silver bromide emulsion (silver bromide -80.0 mol%
, containing 70 g/kg of Ag) to which the blue-sensitive sensitizing dye shown below was added in an amount of 5.0xlO-' mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (1 ps per mole of M halide, OX 10-4 mole) Green-sensitive emulsion layer (4.OX 10 and 4 moles per mole of silver halide) (1 mole of silver halide"tfc I:> 7.OX1
0 mole) (per mole of silver halide 0.9
10-4 mole) For the red-sensitive emulsion layer, the following compound was added at b 2.6 x 10-3 per mole of silver halide.
Mol added.

For the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added at 4.0% per mole of silver halide, respectively.
0XIO'mol, 3.0x10mol, 1.0X10"
”'Mole added.

Further, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added at 1.2xlO mol per mol of silver halide, respectively;
1. lX1o-2 moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (layer structure) The composition of each layer is shown below. The numbers are the coating amount (g/rr1"
), and the silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (T 102) and a blue dye (ulmarine blue)] Layer-1 (blue-sensitive layer) Silver halide emulsion (Br: 80%) 0.26 Gelatin 1.83 Exemplary Couplers (
Y-1) 0.83 color image stabilizer (Cpd-1
) 0.19 solvent (Solv-1)
0.35 Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-2) Third layer (green feeling N) Silver halide emulsion (Br: 80$) Gelatin magenta coupler (Ex M) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Solvent (Solv-2) Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (Solv-3 ) Fifth layer (red-sensitive layer) Silver halide emulsion (Br 0%) Gelatin cyan coupler (ExC) Color image stabilizer (Cpd-6) 0,99 0,08 Polymer (cpct-'y) Solvent (Solv) -4) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Solvent (So 1v-3) Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (denaturation degree 17%) Fluidity Paraffin 0, 40 0, 23 0, 53 0, 21 0, 08 1, 33 0, 17 0, 03 (ExM) Magenta coupler (ExC) Cyan coupler 2:1 mixture (weight ratio) (Cpd-1) Color Image stabilizer (Cpd-2) Color mixture inhibitor H (Cpd-3) Color image stabilizer (CI) d-4) Color image stabilizer H (Cpd-7) Polymer-(CH2-CHh- cONHc4H, Ttl Average molecular weight Go, oo.

(UV-1) 2:9:8 mixture of ultraviolet absorbers (weight ratio) (Cpd-5) Color mixing inhibitor ('Cpd-6) 5:8:9 mixture of color image stabilizers (weight ratio) (Solv -1) Solvent (Solv-2) 2:1 mixture (volume ratio) of solvent (5olv-3) Solvent (5olv-4) Solvent The coating liquids of the 1st to 7th layers are mixed with a wJ with a balance of surface tension and viscosity. After cutting and coating, a multilayer silver halide color photographic material was prepared.

This photosensitive material was designated as sample 200.

Next, light-sensitive materials Samples 201 to 210 were prepared in exactly the same manner except that the yellow coupler was changed as shown in Table 3. The amount of yellow coupler added is sample 200.
(sample 207 has 172 moles),
The floor a for sensitometry on these samples! After exposure, development processing was performed using the following processing steps.

After exposing the above photosensitive material through an optical wedge, it was processed in the following steps.

凰mi-瓜 翫-zuri color development 30℃ 1 minute 40 seconds bleach fixing
30-34℃ 1 minute 00 seconds rinse 030-34℃
Rinse for 20 seconds ■ Rinse for 20 seconds at 30-34℃ ■ Dry for 20 seconds at 30-34℃ Dry for 20 seconds at 70-80℃ (3-tank countercurrent method from rinse ■ → ■) The composition of each treatment solution is as follows. It is.

Soomi
1 diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0 g nitrilotriacetic acid 2.0 g triethylene diamine (
1゜4-diazabicyclo(2゜2.2]octane) s, 0g potassium bromide 0.5g potassium carbonate
30gN-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5gdiethylhydroxylamine 4.0gFluorescent brightener (UVITEX-(manufactured by Ciba-Geigi) 1.5g Add water to 1000Tn[lpH(
25°C) 10.251 Wataru I water 400d Ammonium thiosulfate (70%) 200d Sodium sulfite 20g Iron ethylenediaminetetraacetate (
m) Ammonium Bog disodium ethylenediaminetetraacetate Add 10g water
1000 pH (25℃)
7.00 Rinse liquid ion exchange water (calcium, magnesium 3pp each
m or less) The yellow color development of these samples is 11 degrees (Dmax).

The sensitivity and fog are shown in Table 3. The sensitivity is expressed as the relative value of the exposure amount that gives a density of 0.8, with sample 200 being 100.

In addition, in order to investigate the storage stability of yellow dye images, dye image storage tests were conducted at the request of (a) and (b) below.

(a) Photobleaching xenon fade meter 8.5XIO4 lux 100 hours (b) Dark fading 60°C 70% RH 40 days 1 Dye image storage stability is the density after the test (D ) expressed as a percentage (%).

These results are shown in Table 3.

From Table 3, sample 200 containing the yellow coupler of the invention
It is clear that all of Samples 207 to 207 exhibit good color development and are excellent in both light and moist heat storage properties.

Hand-selling amendment (voluntary) April 14, 1989 1. Indication of the case 1988 Patent Application No. 216697 2. Name of the invention Silver halide color photographic light-sensitive material 3. Person making the amendment Relationship with the case Patent applicant address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd. Representative: Minoru Ohnishi 4, Agent address: 7th Floor, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo 105, Column 7 of "Detailed Description of the Invention" in the Specification; Contents of the amendment (1) Changed “foregoing” from line 7 of page 53 of the specification to “aforementioned”
will be corrected.

(2) rlooJ on page 77, line 8 of the same book as rloI
Correct to J.

(3) rlooJ in the 7th line from the bottom of page 84 of the same book.
Corrected to lolJ.

(4) Correct the structural formula of the compound in the "blue-sensitive emulsion layer" on page 87, line 2 of the same book as follows.

” (that's all)

Claims (1)

[Scope of Claims] A silver halide color photographic material, characterized in that at least one layer on a support contains at least one coupler represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, [A_1] represents a coupler residue from which one hydrogen atom at the coupling position has been removed, and X_1 is -SO_2N
Represents a group represented by H- or -NHSO_2-, R
_1 represents an alkyl group or a phenyl group, R_2 is a nitro group, a cyano group, a trifluoromethyl group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group,
or represents an alkoxycarbonyl group, R_3 represents a substitutable group other than a hydroxyl group, l represents an integer of 1 to 5, and m represents 0, 1, 2, 3 or 4. )