JPH0473771B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to color photographic materials containing novel couplers. (Background Art of the Invention) To form a color photographic image based on a subtractive color method, an aromatic primary amine compound, particularly an N,N-disubstituted paraphenylenediamine compound, is used as a developing agent, and is exposed to light or chemically fogged. A process is utilized in which cyan, magenta, and yellow dye images are produced by reducing the silver halide grains of a photographic emulsion and simultaneously reacting the oxidation products of the developing agent with the coupler. The coupler for the above color development method is a compound having a phenolic hydroxyl group, an aniline amino group, an active methylene group or an active methine group, and provides a dye by oxidative coupling with an aromatic primary amine developing agent. . Couplers that react with oxidized color developing agents to form cyan dyes include phenols and naphthols. Couplers that form magenta dyes include pyrazolone, pyrazolotriazole, pyrazolobenzimidazole, indazolone, cyanoacetophenone, and thiaminoaniline. Couplers that form yellow dyes include alpha acylacetamide, acetoacetate, beta diketone, and N,N-
Examples include malondiamide. Various methods have been devised for adding couplers such as those mentioned above to photographic emulsion layers.
Introducing a lipophilic ballast group into the coupler molecule,
A method in which the compound is added by dissolving it in an organic solvent and emulsifying it is useful. The following properties are necessary for a coupler having a lipophilic ballast group in order to produce a color light-sensitive material with excellent photographic performance. That is, (1) the coupler and the coloring dye produced during color development have high solubility in the high-boiling organic solvent used for dispersing the coupler (for example, tricresyl phosphate); (2) High stability after dispersion in a silver halide photographic emulsion, and a stable coating film without precipitation of coupler crystals even after coating and drying on a support. (3) It has excellent diffusion resistance and does not diffuse to other layers. (4) Good dyeability, excellent spectral absorption characteristics of the dyed dye image, and high color, density, and fastness to light of the dye image. (5) Easy synthesis from inexpensive raw materials with good reproducibility;
and can be obtained in high yield. etc. Conventionally, many attempts have been made to modify the structure of the ballast group in order to improve these properties. As an example of these attempts,
No., Special Publication No. 46-5391, Special Publication No. 39-27563, U.S. Patent No. 2589004, U.S. Patent No. 2908573, U.S. Pat.
No., US Patent No. 2474293, US Patent No. 2039970, US Patent No. 2920961, Special Publication No. 1974-36078, US Patent No.
No. 2589040, Brit No. 944838, Special Publication No. 1977-19026,
U.S. Patent No. 2659329, Brit No. 1813832, JP-A-53-
No. 76834, JP 54-36856, JP 53-82411
No., OLS2707488, JP 53-139534, JP 53-141622, JP 54-23528, JP 54
−48541, JP-A No. 1983-65035, JP-A-1983-
No. 99433, JP-A-54-121126, etc. can be mentioned. However, conventionally known couplers having a ballast group have some defects and do not fully satisfy the above-mentioned necessary properties. these,
Couplers with lipophilic ballast groups are superior to couplers of other series (for example, those with acid groups) in terms of stability in the emulsion layer, diffusion resistance, spectral absorption characteristics of color images, fastness of color images, and suitability for synthesis. Although many of them are superior to couplers added to the emulsion layer as a micellar aqueous solution), no one has yet been found that is satisfactory in terms of color development. In high-temperature rapid processing, which has recently become popular, color development is particularly important, and insufficient color development becomes a serious problem. 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, during the development process, it is absorbed into the emulsion layer, so the amount in the developer decreases, resulting in a decrease in color development. It is carried into bleach or bleach-fix solutions, inhibiting desilvering and reducing dye density. It remains in the photosensitive material after processing and reduces color image fastness. B, O, D,
It causes an increase in C・O・D. It is highly desirable to remove or reduce the amount of organic solvents used to promote color development. (Objective of the Invention) The first object of the present invention is to provide a coupler suitable for producing a color photographic light-sensitive material having excellent photographic properties, especially coloring properties. The second object of the present invention is to use a coupler having a novel substituent, so that even if a small amount of high boiling point organic solvent is used for dispersing the coupler, there is no precipitation of coupler crystals and sufficient color development is achieved. An object of the present invention is to provide a coupler photographic material. The third object of the present invention is to provide a coupler photograph with sufficient color development even when organic solvents for promoting color development such as benzyl alcohol are removed or reduced from a color developer by using a coupler having a novel substituent. Our purpose is to provide photosensitive materials. A fourth object of the present invention is to provide a color photographic material suitable for rapid processing at high temperatures by using a new coupler. (Disclosure of the Invention) These objects of the present invention have been achieved by a silver halide color photographic light-sensitive material containing a coupler having a diffusion-resistant group represented by the following general formula (). General formula () In the formula, R is an aliphatic group having 8 to 18 carbon atoms (e.g., n-decyl group, n-tetradecyl group, n-octyl group, t-octyl group, n-octadecyl group, n-octenyl group, 8-chloro octyl group)
, and Z is a divalent aliphatic group having 1 to 7 carbon atoms (e.g., methylene group, 1,1-propylene group,
Ethylene group, 1,3-propylene group, 1,6-hexylene group, hexylmethylene group, 1,2-cyclohexylene group, 2-(2'-chloroethyl)-1,
3-propylene group), and Y represents a hydrogen atom, a methyl group or a chloro atom. Any of the known coupler groups of the above-mentioned coupler having a diffusion-resistant group can exhibit the effects of the present invention. Preferred examples include phenol and naphthol as cyan coupler residues, pyrazolone, pyrazoloimidazole, pyrazolotetrazole, pyrazolopyrazole, pyrazolotriazole, pyrazolobenzimidazole, indazolone, cyanoacetophenone, and 4-aminoaniline, yellow coupler residues include alphaacylacetamide, betaketoacetate, betadiketone, and N,N
- Malondiamide, etc. can be mentioned. 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 addition, examples of the coupler residue that reacts with the oxidized color developing agent to form a colorless compound include indanone, acetophenone, and the like. The coupler residue may have a substituent other than a hydrogen atom at a position (coupling position) that causes a coupling reaction with the oxidized color developing agent. Among the couplers of the present invention, those useful are represented by the following general formula () or (). General formula () General formula () In the formula, R, Y and Z have the same meanings as defined in the general formula (), A represents a coupling group, and X represents an organic residue bonded to the coupling position of the coupling group A. In the formula, when A represents a yellow image-forming coupling group, it specifically refers to pivalylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malonester monoamide type, Benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, heterocyclic acetamide contained in U.S. Pat. Coupler residue derived from ring-substituted acetate or U.S. Patent No. 3770446, U.S. Patent No. 1459171, West German Patent (OLS) No. 2503099, Japanese Published Patent No. 50-
No. 139738 or Research Disclosure
Examples include coupler residues derived from acylacetamides described in No. 15737 and heterocyclic coupler residues described in US Pat. No. 4,046,574. When A represents a magenta color image forming coupling group, specifically 5-oxo-2-pyrazoline type,
Examples include pyrazolobenzimidazole type, pyrazolotriazole type, cyanoacetophenone type, and N-heterocycle-substituted acylacetamide type coupler residues described in OLS No. 3121955. When A represents a cyan image-forming coupling group, mention may be made of coupler residues having a phenol nucleus or an alpha-naphthol nucleus. When A represents a coupling group that does not substantially form a dye, examples of this type of coupler residue include indanone type and acetophenone type coupler residues, and specifically, US Pat. No. 4,052,213;
Same No. 4088491, No. 3632345, No. 3958993, Same No.
It is described in No. 3961959, No. 4046574, or No. 3938996. As X bonded to the coupling position of the coupler, a known coupling-off group can be used in the general formula (). In the general formula (), X may be a known leaving group or a hydrogen atom. The leaving group used in the general formula () is an atomic group bonded to the coupling position of the coupler component A with a nitrogen atom, oxygen atom, carbon atom, or sulfur atom, and in addition, in the general formula (), it is a halogen atom. is described below. Alkoxy group, acyloxy group, aryloxy group, arylthio group, heterocyclic thio group, alkylthio group, sulfonamide group, heterocyclic oxy group, nitrogen-containing 5- or 6-membered heterocyclic group (at least one nitrogen atom It contains an atom and bonds to the active position of the coupler moiety through a nitrogen atom.For example, imidazolyl group, triazolyl group, 2,
4-dioxoimidazolidinyl group, 3,5-dioxo-1,2,4-triazolidinyl group, pyrazolyl group, etc.), benzene-fused ring heterocyclic group (e.g. benzotriazolyl group, benzimidazolyl group, etc.), arylazo group , chlorine atom, aliphatic aminomethyl group, etc. When these leaving groups are X in the general formula (), they may have the following substituents at substitutable positions, and through those which can be divalent groups among the following substituents: , or directly has a group of general formula (). Furthermore, when the aforementioned leaving group is X in the general formula (), they may have the following substituents at substitutable positions. Number of carbon atoms: 1 to 32, preferably 1
~10 saturated or unsaturated, cyclic, straight chain, or branched substituted or unsubstituted alkyl groups, with ~6 carbon atoms
10 aryl groups, halogen atoms, cyano groups, nitro groups, nitroso groups, carboxy groups, carbamoyl groups, sulfo groups, hydroxy groups, amino groups, sulfamoyl groups, ureido groups, with 1 to 32 carbon atoms, preferably 1 to 10 (or less) (same as above) alkoxy group, acylamino group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylsulfonamide group, N-alkyl (or N,N-dialkyl)
Sulfamoyl group, N-alkyl (or N,N
-Dialkyl)carbamoyl group, alkanesulfonyl group, alkanoyl group, alkanoyloxy group, alkylthio group, carbon number 6-10 (the same applies below)
aryloxy group, aryloxycarbonyl group, arylsulfonamide group, N-arylsulfamoyl group, arylsulfonyl group, arylthio group, arylcarbonyl group, N-arylcarbamoyl group, arylureido group or aryloxycarbamoyl group, etc. be. Further, the present invention is particularly effective because in the general formulas () and (), A is the following general formula (),
(), (), (), (), (), (), (
),
When it is a coupler residue represented by (), () or (). These couplers are preferred because of their high coupling speed. 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 ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
When R ₇ , R ₈ , R ₉ , R ₁₀ or R ₁₁ contains a diffusion-resistant group other than the diffusion-resistant group of the present invention, it is selected such that the total number of carbon atoms is 8 to 32, preferably 10 to 22;
Otherwise, the total number of carbons is 15 or less, preferably 10 or less. In the formula, R ₁ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R ₂ and R ₃ each represent an aromatic group or a heterocyclic group. In the formula, the aliphatic group represented by R ₁ preferably has 1 to 22 carbon atoms and may be substituted or unsubstituted, chain or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R ₁ are:
Such as: isopropyl, isobutyl, tert-butyl, isoamyl, 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-(phthalimido)isopropyl group,
α-(benzenesulfonamido)isopropyl group, etc. R ₁ , R ₂ or R ₃ is an aromatic group (especially phenyl group)
In this case, 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. , an alkyl-substituted succinimide group, etc., and 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, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., and the aryl of these substituents The radical moieties may be further substituted with one or more alkyl groups having a total of 1 to 22 carbon atoms. The phenyl group represented by R ₁ , R ₂ or R ₃ further includes an amino group, including one substituted with a lower alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, It may be substituted with a thiocyano group or a halogen atom. Furthermore, R ₁ , R ₂ or R ₃ 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, and the like. These substituents may themselves have further substituents. When R ₁ represents an alkoxy group, the alkyl portion has 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
represents a straight-chain or branched-chain alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group, which may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like. When R ₁ , R ₂ or R ₃ represents a heterocyclic group,
Each of the heterocyclic groups is bonded to the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group through one of the carbon atoms forming the ring. Such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyritidine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine,
An example is oxazine. These may further have a substituent on the ring. In the formula, R ₅ has 1 to 32 carbon atoms, preferably 1
to 22 straight-chain or branched alkyl groups (e.g. methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g. allyl), cyclic alkyl groups (e.g. cyclopentyl, cyclohexyl, norbornyl) ), aralkyl groups (e.g., benzyl, β-phenylethyl, etc.), cyclic alkenyl groups (e.g., cyclopentenyl, cyclohexenyl, etc.), and these represent halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy groups, Aryloxy group, carboxy 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 or the like. Furthermore, R ₅ is an aryl group (e.g. phenyl group,
(α- or β-naphthyl group, etc.) may also be represented. 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,
Aryl group, alkoxy group, aryloxy group,
Carboxy 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-
It may have an arylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group, etc.
More preferred as R ₅ is phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. It is useful because there are few colors. Furthermore, R ₅ 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, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group) , oxazolyl group, imidazolyl group, naphthoxazolyl group, etc.), a heterocyclic group substituted with the substituents listed for the above aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, It may also represent an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group. In the formula, R ₄ is a hydrogen atom, a straight or branched alkyl having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms,
alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (which may have the substituents listed above for R ₅ ), aryl groups and heterocyclic groups (which may have the substituents listed above for R ₅ ); ), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.),
Aryloxycarbonyl group (e.g. phenoxycarbonyl group, naphthoxycarbonyl group, etc.),
Aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy, ethoxy, heptadecyloxy, etc.), aryloxy groups (e.g., phenoxy, tolyloxy, etc.), alkylthio groups (e.g., ethylthio, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, 3-[(2,4-di-
tert-amylphenoxy)astamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylpropionamide group, etc.), N-aryl-lyacylamino group (e.g., N-phenylacetamide group, etc.) , ureido groups (e.g. ureido, N-arylureido,
N-alkylureido group, etc.), urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-
5-tetradecanamide anilino group, etc.), alkylamino groups (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino groups (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino groups (e.g. 4-pyridylamino group, 2-benzoxazolylamino group, etc.), alkylcarbonyl group (e.g., methylcarbonyl group, etc.), arylcarbonyl group (e.g., phenylcarbonyl group, etc.), sulfonamide group (e.g., alkylsulfonamide group, aryl sulfonamide group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g., N-alkylsulfamoyl, N,N-
dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.), cyano group, hydroxy group, mercapto group, halogen atom, and a sulfo group. In the formula, R ₆ is a hydrogen atom or a carbon number of 1 to 32,
It preferably represents 1 to 22 straight-chain or branched-chain alkyl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups, or cyclic alkenyl groups, which may have the substituents listed for R ₅ above. Furthermore, R ₆ may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R ₅ above. R ₆ 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, an 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- It may also represent an acylanilino group, a hydroxy group or a mercapto group. R ₇ , R ₈ and R ₉ each represent a group used in a typical 4-equivalent phenol or α-naphthol coupler; specifically, R ₇ is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic carbonized Hydrogen residue, N-arylureido group, acylamino group, -O-R ₁₂ or -S
-R ₁₂ (wherein R ₁₂ is an aliphatic hydrocarbon residue), and when two or more R ₇ exist in the same molecule, the two or more R ₇ may be different groups. Group hydrocarbon residues include those having substituents. In addition, when these substituents contain an aryl group,
The aryl group may have the substituents listed for R ₅ above. R ₈ and R ₉ can include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a water atom; Including those with substituents. Further, R ₈ and R ₉ may jointly form a nitrogen-containing heterocyclic nucleus. l is an integer of 1 to 4, m is an integer of 1 to 3, and n is an integer of 1 to 5. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic.
Preferred are alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (e.g., allyl, octenyl, etc.). . Typical 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, hydroxy, carboxyl, amino, substituted amino,
Examples include groups such as sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. R ₁₀ is an arylcarbonyl group, carbon number 2-32,
Preferably 2-22 alkanoyl group, arylcarbamoyl group, carbon number 2-32, preferably 2-22
represents an alkanecarbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, and these may have a substituent such as an alkoxy group, an alkoxycarbonyl group, or an acylamino group. ,
Examples include an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsacinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, and an aryl group. R ₁₁ is an arylcarbonyl group, carbon number 2-32,
Preferably 2-22 alkanoyl group, arylcarbamoyl group, carbon number 2-32, preferably 2-22
Alkanecarbamoyl group, alkoxycarbonyl group or aryloxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, alkanesulfonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, arylsulfonyl group, aryl group, 5-membered or a 6-membered heterocyclic group (the hetero atom is selected from a nitrogen atom, an oxygen atom, and a sulfur atom, such as a triazolyl group, an imidazolyl group, a phthalimide group, a succinimide group, a furyl group, a pyridyl group, or a benzotriazolyl group) and these are the above
It may have the substituents mentioned in _R10 . As the atomic group represented by X in the general formulas () and (), the following are particularly preferred in combination with the coupler core because of their high coupling rate. In other words, the atomic groups bonded to the coupling positions of general formulas () and () are 2,4
-dioxoimidazolidinyl group, 3,5-dioxotriazolidinyl-4-yl group, 2,4-dioxooxazolidinyl group, imidazolyl group, pyrazolyl group, triazolyl group, benztriazolyl group , phenoxy group, arylthio group, tetrazotetrazolylthio group, alkylthio group, alkoxy group, alkyloxy group, and the atomic group bonded to the coupling position of the general formula () and (), (), () is an imidazolyl group. , pyrazolyl group,
triazolyl group, benztriazolyl group, arylthio group, tetrazolylthio group, phenoxy group,
an alkoxy group, acyloxy group, alkylthio group, arylazo group or chlorine atom,
The atomic groups bonded to the coupling positions of general formulas (), () and () include alkoxy groups,
A phenoxy group, an arylazo group, an arylthio group, a chloro atom, a tetrazolylthio group, an acyloxy group, or an alkylthio group, and the atomic groups bonded to the coupling position of general formulas () and () include a tetrazolylthio group, a benztriazolyl group, and a pyrazolyl group. group, arylthio group, arylazo group or phenoxy group. These leaving groups can have the substituents listed as substituents for X in general formulas () and (). A suitable amount of the coupler of the invention to be used is from 1 x 10 ^-3 to 5 x 10 ^-1 mol per silver mol, preferably 1 x
10 ⁻² to 5×10 ⁻¹ mol. Examples of couplers used in the present invention are listed below. However, it is not limited to these. The oil-solubilizing group of the present invention can generally be synthesized by the following synthetic route. In the above formula, Y, R and Z have the same meanings as explained in the general formula (). W represents a bromine or chlorine atom. In the reaction of introducing the above carboxylic acid into the coupler part, it is common to perform an esterification reaction using a dehydration condensation agent such as dicyclohexylcarbodiimide using a hydroxyl group prepared in advance at the oil-solubilizing group introduction position of the coupler part. be. Synthesis Example (1) Synthesis of Exemplary Coupler (1) Synthesis was carried out by the following synthesis route. Step Synthesis of Compound 2 Mix 16.8 g of Compound 1 in 120 ml of toluene, add 15 g of sodium methoxide to this solution, and heat at 80°C.
heated to. 14.8g of bromoacetic acid was added dropwise to this. After reacting for 2 hours, let it cool and add 1N diluted hydrochloric acid 200
ml was added and transferred to a separating funnel. The oil layer was concentrated by repeated washing with water until it became neutral. The residue was recrystallized from hexane to obtain 11 g of Compound 1. Step Preparation of coupler (1) 11 g of compound 1 obtained in step and compound 3
Take 8.7g of and add 20ml of N,N-dimethylformamide.
dissolved in Add to this solution under stirring at room temperature (25°C),
A solution of 3.7 g of N,N'-dicyclohexylcarbodiimide dissolved in 10 ml of acetonitrile was added dropwise.
After reacting for 3 hours, the precipitated N,N'-dicyclohexylurea was separated. Ethyl acetate 500%
ml was added and water washing was performed three times. The oil layer was concentrated to obtain 13.7 g of the desired coupler (1) in the form of an oil. Synthesis example (2) Synthesis of coupler (2) 2-{3-(4-cyanophenylureido)-5
-heptafluorobutanamide-4-{3-(2-
hydroxyethoxy)phenoxy}phenol,
31g and compound 1 obtained in the step of synthesis example (1),
Mix 15.3g with 100ml of acetone and add N,
A solution of 10.3 g of N'-dicyclohexylcarbodiimide dissolved in 20 ml of acetone was added dropwise at room temperature. After reacting for 2 hours, by-produced N,N'-dicyclohexylurea was filtered off, and the filtrate was concentrated. 43.3g of the desired coupler (2) in the form of an oil was obtained. Synthesis example (3) Synthesis of coupler (14) 4-(2-dodecylphenoxy)butanoic acid, 10.6 g, and 3-{2-chloro-5-
(2-hydroxyethylcarbamoyl)anilino}
-1-(2,4,6-trichlorophenyl)-5-
12.4 g of the desired coupler (14) was obtained in the same manner as in Synthesis Example (2) using 14.3 g of pyrazolone and N,N'-dicyclohexylcarbodiimide. However, crystallization was performed using a mixed solvent of ethyl acetate and hexane. In the present invention, the coupler can be introduced into the silver halide emulsion layer using known methods, such as those disclosed in the US Pat.
The method described in No. 2322027 is used. For example, phthalic acid alkyl esters (dipterphthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.)
dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate),
benzoic acid esters (e.g. octyl benzoate),
Alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesates (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 30°C to 150°C, e.g. Lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-
After being dissolved in ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 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. Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used alone or in conjunction with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. Arthur for details on how to make gelatin. The Macromolecular Chemistry of Gelatin, by George Weiss (Academic Press,
Published in 1964). Examples of the hydrophilic colloids that can be used include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethylcellulose;
Cellulose derivatives such as carboxymethyl cellulose and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl There are a wide variety of synthetic hydrophilic polymeric materials such as imidazole, polyvinylpyrazole, etc., single or copolymers. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
Expressed as an average based on projected area. ) is not particularly limited, but it is preferably 3μ or less. The particle size may be narrow or wide. The silver halide grains in the photographic emulsion may have regular crystal structures such as cubic or octahedral shapes, or may have irregular crystal structures such as spherical or plate shapes, or may have irregular crystal structures such as spherical or plate shapes. It can also be a composite of shapes. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZeIiKman et al.
Making and Coating Photographic Emulsion
(The 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 be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may 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. Two or more types 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, etc. may be allowed to coexist. After forming a precipitate or physically ripening the emulsion, soluble salts are usually removed. For this purpose, the long-known Nudel water washing method, which involves gelling gelatin, may be used, or polyvalent anions can be used to remove soluble salts. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A flocculation method may also be used. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die
Grundlagender Photographischen Proresse
mit Silber−halogeniden” (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, methicaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthione; azaindenes, e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds obtained as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast , sensitization)
Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or releasable synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. For the photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions, such as those described in Research Disclosure No. 176, pages 28-30, can be applied. can do. The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or above 50°C. As the fixer, one 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 fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., 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-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N −
β-methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
P226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, It may also contain a fogging agent such as sodium boron hydride, an auxiliary developer such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper (), peracids, quinones, nitrone compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Complex salts of aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Permanganate; nitrosophenol, etc. can be used. Among these, potassium ferricyanide, sodium ethylenediaminetetraacetate, and ammonium ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid complexes are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are 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 commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, chitrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.
These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobalpituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. The present invention
It is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually include a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected according to need. a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer,
It is usual that each blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In the same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material produced using the present invention, in addition to the coupler represented by the above general formula [], other dye-forming couplers, that is, color development processing In this method, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative or an aminophenol derivative) may be used. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloimidazole couplers, pyrazolo pyrazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumaron couplers, open-chain alkyacetonitrile couplers, etc. Examples of yellow couplers include acylacetamide couplers (eg, benzoylacetanilides and pivaloylacetanilides), and examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized.
The coupler is 4-equivalent or 2-equivalent to silver ion.
Either equivalence is acceptable. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor.
In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. The coupler of the present invention and the above-mentioned couplers can be used in combination in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added in two or more different layers. Of course it doesn't matter. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, 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 (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers. The photosensitive material produced 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 preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, 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. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. Example 1 A multilayer color photosensitive material consisting of layers having the composition shown below on a transparent cellulose triacetate film support was prepared, and this was designated as Sample 101. 1st layer: Anti-halation layer Gelatin layer containing black colloidal silver...0.18g/m ² Ultraviolet absorber C-1...0.12g/m ² C-2...0.17g/m ² 2nd layer: Intermediate layer 2, 5-di-t-pentadecylhydroquinone...0.18g/ ^m2 Coupler C-3...0.11g/ ^m2Silver iodobromide emulsion (silver iodide 1 mol% average grain size 0.07μ)...0.15g/ ^m2 Gelatin layer 3rd layer containing: 1st red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol% average grain size 0.6μ)...0.72g/ ^m2 Sensitizing dye...7.0×10 per mole of silver ^-5 mol Sensitizing dye...2.0 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...2.8 x 10 ^-4 mol per 1 mol of silver Sensitizing dye...2.0 x 10 ^-5 per 1 mol of silver Gelatin layer containing mole coupler C-4...0.093g/ ^m2 coupler C-5...0.31g/ ^m2 coupler C-6...0.010g/ ^m2 Fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide 10 mol%, average grain size 1.5 μ) …1.2 g/m ² Sensitizing dye … 5.2 × 10 ^-5 mol per mol of silver Sensitizing dye … 1.5 × 10 ^-5 per mol of silver Mol Sensitizing dye...2.1 x 10 ^-4 mol per mol of silver Sensitizing dye...1.5 x 10 ^-5 mol per mol of silver Coupler C-4...0.10g/ ^m2Coupler C-5...0.061g /m ² Gelatin layer containing coupler C-7 ...0,046 g/m ² 5th layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol% average grain size 2.2 μ) ...2.0 g/m 2 ^m2 Sensitizing dye...5.5 x 10 ^-5 mol per mol of silver Sensitizing dye...1.6 x 10 ^-5 mol per mol of silver Sensitizing dye...2.2 x 10 ^-5 mol per mol of silver Sensitizing dye...1.6×10 ^-5 mol per mol of silver Coupler C-5...0.044 g/m ² Coupler C-7...0.16 g/m ² Gelatin layer 6th layer: Intermediate layer Gelatin layer 7 Layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.5 μ)...0.55 g/ ^m2 Sensitizing dye...3.8 x 10 ^-4 mol per mol of silver Sensitization Dye...3.0 x 10 ^-5 mol per mol of silver Sensitizing dye...1.2 x 10 ^-4 mol per mol of silver Coupler C-8...0.29g/m ² Coupler C-9...0.040g/m ² Coupler C-10...0.055g/m ^2Coupler C-11...0.058g/ ^m 28th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol% average grain size 1.5μ)...1.0 g/m ² Sensitizing dye...2.7×10 ^-4 mol per 1 mol of silver Sensitizing dye...2.1×10 ^-5 mol per 1 mol of silver Sensitizing dye...8.5×10 ^- per 1 mol of silver ⁵ mol coupler C-8...0.25g/m ² coupler C-9...0.013g/m ² coupler C-10...0.009g/m ² coupler C-11...0.011g/m ² Gelatin layer 9th layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 2.2μ)...1.2 g/ ^m2 Sensitizing dye...3.0 x 10 ^-4 mol per mol of silver Sensitizing dye... Contains 2.4 x 10 ^-5 mol per mol of silver Sensitizing dye...9.5 x 10 ^-5 mol per mol of silver Coupler C-12...0.070g/ ^m2 Coupler C-9...0.013g/ ^m2 Gelatin layer 10th layer: Yellow filter layer Gelatin layer containing yellow colloidal silver...0.04g/m ² 2,5-di-t-pentadecyl hydroquinone...0.031g/m ² Gelatin layer 11th layer: First blue-sensitive emulsion layer Odor 12th layer of gelatin layer containing silver iodide emulsion (silver iodide 6 mol% average grain size 0.4μ) ...0.32 g/m ² coupler C-13 ...0.68 g/m ² coupler C-14 ...0.030 g/m ² : Second blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol %, average grain size 1.0 μ) …0.29 g/m ² Coupler C-13 … 0.22 g/m ² Sensitizing dye … per mole of silver Gelatin layer 13th layer containing 2.2×10 ^-4 mol: Fine grain emulsion layer Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.15μ) ... 14th gelatin layer containing 0.40 g/m ² : Fine grain emulsion layer 3 Blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 14 mol%, average grain size 2.3 μ) ...0.79 g/m ² Coupler C-13 ... 0.19 g/m ² Sensitizing dye ... 2.3 per mole of silver ×10 ^-4 mol 15th layer: 1st protective layer Ultraviolet absorber C-1...0.14g/m ² Gelatin layer containing ultraviolet absorber C-2...0.22g/m ² 16th layer: 2nd protective layer Poly Methyl methacrylate particles (1.5μ diameter)
...0.05g/ ^m2 Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.07μ) ...Gelatin layer containing 0.30g/ ^m2 In addition to the above composition, gelatin hardener C-
15 and a surfactant were applied. (Samples 102 to 108) Coupler C-7 in the fifth layer of sample 101 was replaced with C-
4, Cp-1, Cp-2 and the coupler of the present invention (13),
Samples 102 to 108 were prepared in the same manner as sample 101 except that (18), (2), and (11) were replaced in equal molar amounts. After imagewise white exposure was applied to Samples 101 to 108, color development was performed as shown below, and the density of the processed samples was measured using a red filter. The fog and sensitivity were determined from these results and were as shown in Table 1. The development processing conditions used here were as follows, and the development was carried out at 38°C. 1 Color development... 2 minutes 45 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing with water... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing with water... 3 minutes 15 seconds 6 Stability... 3 minutes 15 seconds The treatment liquid composition used in each step is as follows. Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate Add 4.5g water to 1l Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt
130g Glacial acetic acid 14ml Add water to 1l Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water to 1l Stabilizer Formalin 8.0ml Add water to 1l

[Table] From Table 1, sample 105 using the coupler of the present invention
-108 shows high sensitivity, indicating that the coupler of the present invention has high color development. Comparative coupler used in Example 1 Example 2 Coupler C-12 in the 9th layer of sample 101 of Example 1
Samples 201 to 206 were prepared in the same manner as sample 101, except that equimolar amounts of were replaced with couplers Cp-3, Cp-4, and the couplers (1), (11), (6), and (19) of the present invention. These samples 101, 201 to 206 were treated in the same manner as in Example 1, and the density of the treated samples was measured using a green filter to determine the fog and density, as shown in Table 2.

【table】

Table 2 shows that the coupler of the present invention has high sensitivity and good color development. The comparative couplers used in this example are as follows.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic material containing a coupler having a diffusion-resistant group represented by the following general formula. general formula In the formula, R represents an aliphatic group having 8 to 18 carbon atoms, Z represents a divalent aliphatic group having 1 to 7 carbon atoms, and Y represents a hydrogen atom, a methyl group, or a chloro atom.