JPH0437421B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photographic material containing a new type of coupler. By color-developing silver halide color photographic materials, the oxidized aromatic primary amine color developing agent and coupler react to produce indophenol, indoaniline, indamine, azomethine, etc.
It is known that phenoxazine, phenazine and similar dyes can be produced to form color images. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming agents, which are complementary colors, respectively. is used. To form a yellow image, for example, acylacetanilide, malondiamide, or dibenzoylmethane couplers are used, and to form a magenta image, pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, or cyanoacetate are mainly used. Phenone or indazolone couplers are used, primarily phenolic couplers such as phenols and naphthols 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 dye image-forming coupler is added to the silver halide emulsion. Couplers added to the emulsion must be non-diffusible (diffusion resistant) in the emulsion binder matrix. Biscoupler that produces two molar equivalents of dye from one molecule of coupler has been known. Among these, certain couplers contain two coupler components in one molecule and only need one diffusion-resistant group, so compared to couplers that contain one coupler component in one molecule, the number of molecules per molar equivalent of the coupler is has a small molecular weight.
Therefore, the molecular weight of the coupler required to form a certain amount of dye density is reduced, and the light-sensitive emulsion layer can be made thinner, and the sharpness of the color image can be improved. Based on this idea, a coupler described in, for example, US Pat. No. 4,248,961 has been proposed. However, known biscouplers are generally inferior to similar couplers containing one coupler moiety in terms of reactivity with oxidized developing agents, and thus have lacked practical use as photographic materials. That is, one mole of a known biscoupler yields less dye than two moles of a similar coupler containing one coupler moiety, and after all, the same concentration cannot be obtained without adding more couplers. Nakatsuta. As a result, there was a loss of sharpness. Furthermore, in the case of known viscouplers, it is difficult to separately control the reactivity of the two active sites with the oxidized developing agent, which limits the intended use. In addition, when a coupler containing one coupling site per mole is generally used which has a high color forming property, the graininess of the obtained color image deteriorates. This is because the amount of dye produced per unit of developed silver increases when a high color forming coupler is used than when a low color forming coupler is used.
That is, in order to obtain a constant density, a highly color-forming coupler requires less developed silver, and a dye cloud of high density is formed per developed silver particle. In other words, when comparing the same density, the dye cloud formed by a coupler with a low color forming property is densely populated with low density ones, and the dye cloud formed by a coupler with a high color forming property is densely populated with a dye cloud formed by a coupler with a high color forming property. It is thought that it exists in patches, resulting in differences in graininess. As a result, as the coloring properties of couplers increase, the graininess of the color images formed deteriorates, and it has been difficult to solve this problem. The present invention relates to a new class of couplers that solves the problems mentioned above. That is, an object of the present invention is to provide a silver halide color light-sensitive material containing a new type of coupler for improving sharpness and graininess. The purpose of the present invention described above is the following general formula ()
This was achieved by a silver halide color photographic material characterized by having a novel coupler represented by on a support. General formula () A-X-B-Y In the formula, A and B each represent a coupler component, and B represents a divalent atomic group that binds to coupler component B at a position other than the position where it couples with oxidized developing agent, and Y represents an atomic group that binds to coupler component B at a position where coupler component B couples with oxidized developing agent; Represents a hydrogen atom or a halogen atom. Since the coupler of the present invention is used by being added to an emulsion, it must be resistant to diffusion. A diffusion-resistant group is an organic group that makes the coupler molecule sufficiently large to render the coupler substantially non-diffusible from the layer to which it is coated. Therefore, in the general formula (), at least one of A, X, B and Y contains a diffusion-resistant group. It is preferable for the diffusion-resistant group to have the minimum necessary size because the molecular weight can be reduced. The diffusion-resistant group is A,
Only one of X, B, or Y may exist, or two or more may exist dispersedly. However, if two or more of them exist dispersedly, each of them does not need to be diffusion-resistant, and generally It suffices if the coupler represented by the formula () is resistant to diffusion as a whole. In the general formula (), coupler components A and B
is a coupler component that contains a group that can react with the oxidized developing agent and forms a dye, and a coupler component that forms an alkali-soluble dye that is washed away into the processing solution even if the dye is formed. Alternatively, it represents a coupler component that does not substantially form a dye (colorless coupler). In the general formula (), any known ones can be used for X and Y. X and Y may each be a group that can leave or a group that cannot leave after the coupler components A and B undergo a coupling reaction with the oxidized developing agent. When X and Y are leaveable groups, each is a photographically inert group or a photographically useful group. When X or (and) Y represent a photographically useful group, the coupler of the present invention can have the desired performance of each photographically useful group in addition to the effects of the present invention.
For example, if the reagent is a development inhibitor, it can be used to inhibit the development of silver halide and is commonly known as a DIR coupler. For example, if the photographically useful group is a development accelerator, it can be used for the purpose of accelerating the development of silver halide. Further, if the photographically useful group is a silver halide solvent, it is used for the purpose of promoting dissolution of silver halide. Furthermore, when the photographically useful group is a dye,
They can be used for color correction purposes and are commonly known as colored couplers. The present invention encompasses the group of couplers described above, but when the ballast group is A-X-B-Y, it has a sufficient size and one coupling reaction occurs to form the dye moiety and the remaining coupler moieties. When separated or when two coupling reactions occur simultaneously, 2
A coupler whose distribution of ballast groups is controlled so that when divided into two dye moieties, at least one of the two dye moieties has a ballast group large enough to cause slight diffusion, has a granular property. This is particularly advantageous in that the degree of improvement is large. It is believed that the reason why the coupler of the present invention exhibits excellent performance in terms of sharpness and graininess is as follows. One molecule of the coupler of the present invention can undergo a coupling reaction with two oxidized developing agents, A and B.
When is a coupler component that forms a dye, two different molecules of dye are produced after two coupling reactions. If one or both of the two generated pigments are not made sufficiently diffusion resistant, the pigment will diffuse slightly, causing the pigment cloud to spread appropriately and overlap with neighboring pigment clouds. As a result, graininess becomes less noticeable. It is thought that the sharpness will naturally deteriorate as the dye diffuses and the dye cloud becomes larger, but by appropriately selecting the substituents on the individual coupler moieties and changing the molecular weight of the dye, it is possible to appropriately adjust the diffusivity. The situation did not get worse, but rather improved. because,
The coupler of the present invention contains two coupler components in one molecule, and only one diffusion-resistant group is required.
The molecular weight per molar equivalent of the coupler is small compared to a coupler containing two coupler components. Therefore, the light-sensitive emulsion layer could be made thinner, and the sharpness of the color image was better than expected. One molecule of the coupler of the present invention can undergo a coupling reaction with two oxidized developing agents separately.
Therefore, the outer coupler may be released by the first coupling reaction. For example, when only coupler component A contains a diffusion-resistant group in general formula (), coupler component A undergoes a coupling reaction with the oxidized developing agent before coupler component B does. At this time, X-B-Y is coupler component A
Since it does not have a diffusion-resistant group, it will diffuse into the emulsion. Next, when coupler component B undergoes a coupling reaction and produces a dye, after all,
It will be understood that the result is the same as if the dye had been diffused from the beginning, as described above, and the graininess could be improved. Granularity may also occur if coupler component A or (and) B either does not substantially form a dye after reacting with the oxidized developing agent, or if it does form a dye, it is washed away into the processing solution. The improvement is significant. This is because it acts as a capture agent for oxidized developing agent, and prevents the color density of a single dye cloud from becoming higher than necessary. The reason why the couplers of the present invention are highly reactive with oxidized developing agents is also believed in the discussion below. That is, couplers are generally dissolved in dispersing oil and present in the emulsion as fine oil droplets. The developing agent added to the developer is water-soluble, and the oxidized developing agent is even more water-soluble. Therefore, one obstacle is the process in which the oxidized developing agent is incorporated into the oil droplets to react with the coupler. In this process, the couplers of the present invention produce a desirable change because they form diffusible couplers or dyes. As mentioned above, the couplers of the present invention produce slightly diffusing couplers or dyes during color development processing. This means that the coupler or dye maintains a relationship in the partition equilibrium between the oil layer and the water layer.
It means going back and forth between the oil layer and the water layer. When the coupler or dye reenters the oil droplets, it entrains the oxidized developing agent into the oil droplets, increasing the frequency of encounters between the oxidized developing agent and the coupler. This is interpreted as apparently increasing the reactivity of the coupler of the present invention with the oxidized developing agent. In the coupler of the present invention, A, X, B and Y can be selected from a wide range, and depending on the selection, the coupler can be used in various known methods in various sensitive materials (for example, color negative film, color reversal film, color positive film). It can also be used as a main coupler in high-sensitivity layers or low-sensitivity layers,
It is also possible to mix the primary couplers and use them as DIR couplers, colored couplers, or competitive couplers. It is possible to select the properties of the reaction product with the oxidized developing agent by arbitrary selection of the coupler components A and B (for example, selection of spectral absorption of the dye, formation of a colorless dye), It is possible to select which of the coupler components should be made diffusion resistant (for example, forming a non-diffusible dye or a diffusible dye), and further, by arbitrarily selecting X and Y, the reactivity ratio of the coupler components A and B with the oxidized developing agent can be arbitrarily set. This is because a new function can be added when X or (and) Y is a photographically useful group. The amount of the coupler of the present invention added varies depending on the shape and use of the coupler, but is preferably 1x per mole of silver.
10 ⁻⁶ to 1 mol, particularly preferably 2×10 ⁻³ to 3×
10 ^-1 mole. When A and/or B represent a yellow image-forming coupler residue in the general formula (), pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type , malone ester monoamide type, benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, heterocycle included in U.S. Pat. No. 3,841,880 coupler residues derived from substituted acetamides or heterocyclic substituted acetates or U.S. Pat. No. 3,770,446;
British Patent No. 1459171, West German Patent (OLS) 2503099
Examples include coupler residues derived from acylacetamides described in No., Japanese Publication No. 50-139738 or Research Disclosure No. 15737, and heterocyclic coupler residues described in US Pat. No. 4,046,574. When A and/or B represent a magenta image-forming coupler residue in the general formula (), 5
-Oxo-2-pyrazoline type, pyrazolobenzimidazole type, pyrazolotriazole type, cyanoacetophenone type or West German published patent (OLS)
N-heterocycle-substituted acylacetamide type coupler residues described in No. 3121955 are preferred. When A and/or B in general formula () represent a cyan image-forming coupler residue, a coupler residue having a phenol nucleus or an α-naphthol nucleus is preferred. In the general formula (), when A and/or B represent a coupler residue that does not substantially form a dye, examples of this type of coupler residue include indanone type and acetophenone type coupler residues, and specifically, is U.S. Patent No. 4052213, U.S. Patent No. 4088491
No. 3632345, No. 3958993, No. 3961959,
This is described in No. 4046574 or No. 3938996. In the general formula (), known coupling-off groups and alkyl or aryl groups can be used as the moieties X and Y that bind to the active position of the coupler. Known leaving groups are those that are bonded to the coupling positions of coupler components A and B through nitrogen, oxygen, or sulfur atoms, and groups that are bonded to the coupling position of coupler component B include hydrogen atoms and halogen atoms. For example, groups that leave include sulfonamide groups, heterocyclic oxy groups, nitrogen-containing 5- or 6-membered heterocyclic groups (bonded to the active position of the coupler component via the nitrogen atom), benzene-fused ring groups thereof, phenoxy groups, and arylthio groups. , a heterocyclic thio group, a chlorine atom, an alkylthio group, an arylazo group, an alkoxy group or an acyloxy group. When these leaving groups, alkyl groups and aryl groups are bonded to the active position of coupler component A, they have -B-Y groups as substituents as well as other substitutable positions, and the leaving groups mentioned above, When the alkyl group and aryl group are bonded to the active position of coupler component B, they may have the following substituents at substitutable positions. Saturated or unsaturated, having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms,
Cyclic, straight-chain or branched alkyl group, with 6 or more carbon atoms
10 aryl groups, halogen atoms, cyano groups, nitro groups, nitroso groups, carboxy groups, sulfo groups, hydroxy groups, heterocyclic groups, amino groups, ureido groups,
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,
Examples include N-arylsulfamoyl group, arylsulfonyl group, arylthio group, arylcarbonyl group, N-arylcarbamoyl group, arylureido group, and aryloxycarbamoyl group, which may further have a substituent. Furthermore, the present invention is particularly effective because in the general formula (), A and B are the following general formulas (), (), (), (), (), (), (
),
(), () or (XI). These couplers are preferred because of their high coupling speed. General formula () General formula () General formula () General formula () General formula () General formula () General formula () General formula () General formula () General formula (XI) When the coupler component in the above formula represents A in the general formula (), the free bond derived from the coupling position in the above formula represents the bonding position of -XB-Y. When the coupler component in the above formula represents B in the general formula (), the free bond derived from the coupling position in the above formula represents the bond position of -Y, and AX- represents the bond of R ₁ to R ₁₁ At any bonding position selected from the positions, directly bonding instead of R ₁ to R 11 or R ₁ to R ₁₁ described below
It is bonded through an atomic group selected from among R ₁₁ that can be a divalent group. 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,
Adamantyl group, α-(benzenesulfonamide)
Examples include isopropyl group. 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. , N-alkylsulfamoylamino group,
It may be substituted with an N,N-dialkylsulfamoylamino group, an alkyl-substituted succinimide group, etc. In this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. Phenyl group also includes aryloxy group, aryloxycarbonyl group,
It may be substituted with an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group of these substituents has a total number of carbon atoms of 1 to 22. It may also be substituted with one or more alkyl groups. 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. Further, R ₁ , R ₂ or R ₃ may represent a substituent in which a phenyl group is fused to 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 40 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 heterocyclic group is bonded to the carbon atom of the carbonyl group of the acyl group or the nitrogen atom of the amide group in the alpha acylacetamide through one of the carbon atoms forming the ring. Such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, isodorizine, imidazole, thiazole, oxazole, triazine, thiadiazine,
An example is oxazine. These may further have a substituent on the ring. In the general formula (), R ₅ has a carbon number of 1 to 40,
Preferably 1 to 22 linear or branched alkyl groups (e.g. methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g. allyl group), cyclic alkyl groups (e.g. cyclopentyl group, cyclohexyl group). , norbornyl group), aralkyl group (e.g. benzyl,
β-phenylethyl group, etc.), cyclic alkenyl group (e.g. cyclopentenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, carboxy groups, alkylthiocarbonyl groups. , 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, It may be substituted with an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group, 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, an aryl group, and an alkoxy group. 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,
It may have an N-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.
This is useful because the coupler remaining in the film is less likely to change color due to light or heat. 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 40 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 group (e.g. benzyloxycarbonyl group), alkoxy group (e.g. methoxy group, ethoxy group, heptadecyloxy group etc.), aryloxy group (e.g. phenoxy group, tolyloxy group etc.), alkylthio group (e.g. ethylthio group, 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)acetamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylpropionamide group, etc.), N-arylacylamino group (e.g., N-phenylacetamide group, etc.) , ureido groups (e.g. ureido, N-arylureido, N
-alkylureido group), 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. -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, arylsulfonamide group, etc.), carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, etc.) group, N-
methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g. N-phenylcarbamoyl), sulfamoyl group (e.g.
-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.),
Represents any one of a cyano group, a hydroxy group, a mercapto group, a 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, aromatic ureido group, acylamino group, -O-R ₁₂ or -S-R ₁₂
(However, R ₁₂ is an aliphatic hydrocarbon residue),
When two or more R _7s exist in the same molecule, the two or more R _7s may be different groups, and the aliphatic hydrocarbon residues include those having substituents. Furthermore, when R ₇ is a substituent containing an aryl group, the aryl group may have the substituents listed for R ₅ above. R ₈ and R ₉ may include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom; Including those with substituents. Further, R ₈ and R ₉ may jointly form a nitrogen-containing heterocyclic nucleus. l
is an integer from 1 to 4, m is an integer from 1 to 3, and n is an integer from 1 to 5.
is an integer. 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, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, Examples include groups such as 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 alkylsuccinimide 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 pyridine group, or a benzotriazolyl group). and these are the above
It may have the substituents mentioned in _R10 . As the atomic groups represented by X and Y in the general formula (), the following are particularly preferable in combination with the coupler core because of their high coupling rate. That is, the general formulas () and ()
The atomic group bonded to the coupling position of is 2,
4-dioxoimidazolidinyl group, 3,5-dioxotriazolyl-4-yl group, 2,4-dioxooxazolidinyl group, imidazolyl group, pyrazolyl group, triazolidinyl group, benztriazolyl group , phenoxy group, arylthio group, tetrazolylthio group, alkylthio group, alkoxy group, acyloxy group, or alkyl group, and the atomic group bonded to the coupling position of general formulas (), (), and () is imidazolyl group, pyrazolyl group. , triazolyl group, benztriazolyl group, arylthio group, tetrazolylthio group, phenoxy group, alkoxy group, acyloxy group, alkylthio group, or alkyl group, and is bonded to the coupling position of the general formula (), (), and (). The atomic group is an alkoxy group, phenoxy group, arylthio group, tetrazolylthio group, acyloxy group, or alkylthio group, and the atomic group bonded to the coupling position of general formulas () and (XI) is a tetrazolylthio group, benztriazolyl group. , pyrazolyl group, arylthio group or phenoxy group. When these atomic groups are bonded to the active position of coupler component A, they have -B-Y groups as substituents as well as other substitutable positions, and the aforementioned groups are bonded to the active position of coupler component B. When bonded, they may have the following substituents at substitutable positions. Alkyl group having 1 to 22 carbon atoms, phenyl group, ureido group, halogen atom, cyano group, nitro group, carboxy group, hydroxy group, heterocyclic group,
Alkoxy group with 1 to 22 carbon atoms (the same applies below), alkanesulfonamide group, acylamino group, alkoxycarbonyl group, alkanoyloxy group, alkylthio group, alkoxycarbonylamino group, aryloxy group with 6 to 10 carbon atoms (the same below) , aryloxycarbonyl group, arylthio group, etc., and these may further have a substituent. When Y represents an atom bonded to the coupling position of coupler component B, it is a hydrogen atom, a chloro atom or a fluorine atom. The formula for which the present invention has a particularly large effect is the general formula ()
In this case, A and B are coupling groups represented by the general formula (). In other words, the dye produced by the yellow image-forming coupler generally has a small molecular extinction coefficient and requires a larger amount of coupler to be added than the magenta or cyan image-forming coupler, and since the blue-sensitive emulsion layer is in the uppermost layer, the lower layer The influence of light scattering on Since the coupler of the present invention has a small molecular weight and a small film thickness, the sharpness can be improved. In addition, a development inhibitor which is particularly effective in the present invention is a development inhibitor in which Y represents an optionally substituted benzotriazolyl group or an optionally substituted tetrazolylthio group in the general formula (), and B represents a diffusion-resistant group. When it is a coupling group represented by the general formula () or () without . These couplers have particularly high reactivity and are therefore preferred. Furthermore, when the coupling reaction rate of the BY portion is slightly slower than that of the A-X portion, the degree of sharpness improvement is particularly large and advantageous. The coupling reactivity of couplers is determined by the coupling reactivity of each color image obtained by mixing two types of couplers M and N that give different dyes that can be clearly separated from each other, adding the mixture to an emulsion, and carrying out color development. It can be determined as a relative value by measuring the amount of pigment. The maximum concentration (DM) max. of coupler M, the color development of the concentration DM in the middle stage, and the color development of coupler N (DN) max., the ratio of the reaction activities of both couplers. RM/
RN is expressed by the following formula. RM/RN=log(1-DM/(DM)max.)/log(1
-DN/(DN)max.) In other words, the emulsion containing the mixed coupler is exposed to light at various stages, and several pairs of DM and DN obtained by color development are plotted on two orthogonal axes log ( 1-
The coupling activity ratio RM/RN can be determined from the slope of the straight line obtained by plotting as D/Dmax). Here, by using a fixed coupler N and determining the value of RM/RN for various couplers as described above, the relative coupling reactivity can be determined. It is appropriate to use the following couplers as the above coupler N. for cyan coupler Magenta coupler against yellow coupler Such a coupling rate relationship is satisfied, for example, when X is selected from a pyrazole ring or a triazole ring group, and Y is selected from a benzotriazolyl ring or a tetrazolylthio ring group, and furthermore, among the above, A, B are each general formula ()
It is more preferable that it is represented by or (). Examples of couplers used in the present invention include, but are not limited to, the following compounds. The couplers of the present invention can be synthesized by combining known methods. Generally, it is advantageous to synthesize each part of AX and BY and then connect them. However, A-X
A synthesis route in which -B is synthesized and Y is introduced into it, and a synthesis route in which X-B-Y is synthesized and A is connected thereto may also be selected as appropriate. Specifically, methods for introducing a leaving group into the coupling position of a coupler include U.S. Pat. No. 3,408,194, U.S. Pat.
Same number 3227554, same number 3476563, same number 3311476, same number
No. 3462270, No. 3419391, No. 3876428, No.
No. 3458315, No. 3737316, Japanese Published Patent No. 50-
No. 10728, No. 48-29432, No. 48-73147, No. 49
−122335, No. 51-17438, No. 51-20826, No.
No. 58-18364, No. 50-135310, No. 50-117422,
Examples include the method described in No. 51-26034 or No. 51-21828. Next, we will specifically describe synthesis methods for representative compounds. Synthesis Example 1 Synthesis of Compound (2) The present coupler can be synthesized according to the synthesis scheme shown below. Scheme. Preparation of Compound (c) A mixture of 50 g of (a), 500 ml of acetic acid, and 50 ml of formalin was stirred at room temperature overnight. After cooling the reaction solution, the precipitated solid was filtered, washed with water, and dried to obtain (b)50
I got g. To a mixture of 50 g of (b), 500 ml of toluene, and 10 ml of DMF, 28.8 g of thionyl chloride (SOCl ₂ ) was added dropwise at 50°C. After stirring for an additional 30 minutes, toluene was distilled off to obtain 51 g of (c). Preparation of Compound (e) (d) 18.2 g of sodium hydride (60%) was added to 200 ml of a solution of 46.4 g in DMF. To this, add the DMF solution of (c)
100ml was added dropwise at 30°C. After stirring for an additional hour, the reaction solution was made acidic with hydrochloric acid and extracted. (Vinegar Echi)
By washing the organic layer with water, drying, and concentrating, (e) is precipitated. After this, 73.3g of (e) was obtained. Preparation of Compound (h) (5) A mixture of 47 g, p-toluenesulfonic acid 1 g, ethanolamine 27 g, and xylene 200 ml was heated and refluxed for 3 hours. After removing xylene by distillation, add 1 part of water to it and stir well at room temperature. The solid was filtered and the obtained crude crystals were mixed with methanol.
Reconsolidation yielded 46.5 g of (h). Preparation of coupler (2) (e) 10g, (h) 11.4g, triethylamine 5.1ml
50 ml of a DMF solution containing 6.8 g of dicyclohexylcarbodiimide was added dropwise to 100 ml of the DMF solution at 0°C. After further stirring at room temperature for 24 hours, the reaction solution was cooled, filtered,
The generated urea was removed. Ethyl acetate was added to the solution, washed with water, dried, and recrystallized from ethyl acetate to obtain 10 g of coupler (2). (mp.168.0
~169.0℃) Synthesis Example 2 Synthesis of compound (8) α-(4-methoxybenzoyl)-α-chloro-
2-chloro-5-dodecyloxycarbonylacetanilide, 11.1 g and α-benzoyl-α-
(5-ethoxy-1-methyl-2,4-dioxoimidazolidinyl)-2-hydroxy-5-nitroacetanilide 10.1 g and triethylamine
2.2 g was mixed with 150 ml of acetonitrile and heated under reflux for 2 hours. After cooling to room temperature, it was poured into 500 ml of water and extracted with 500 ml of ethyl acetate. After washing with 1N diluted hydrochloric acid, washing with water was repeated until the solution became neutral. The oil layer was separated and the solvent was distilled off under reduced pressure. 15 g of the desired coupler (8) in the form of an oil was obtained. The analytical sample was purified by column chromatography and its structure was confirmed. The following examples illustrate embodiments and features of the invention, but the scope of the invention is not limited thereto. Examples Preparation of Sample 101 A multilayer color photosensitive material sample consisting of each layer having the composition shown below was prepared on a polyethylene terephthalate film support. 1st layer; anti-halation layer; gelatin layer containing black colloidal silver; 2nd layer; intermediate layer; gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone; 3rd layer; low-sensitivity red-sensitive emulsion layer; Silver emulsion (silver iodide: 5 mol%)...Silver coating amount
1.6g/ ^m2 Sensitizing dye...6 x 10 mol per mol of silver Sensitizing dye...1.5 x 10 mol per mol of silver Coupler EX-1...0.04 mol Coupler EX-5...Silver 0.003 mol for 1 mole Coupler EX-6...for 1 mole of silver
0.0006 mol 4th layer: Highly sensitive red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol%)...Silver coating amount
1.4 g/m ² Sensitizing dye...3 x 10 mol per mol of silver Sensitizing dye...1.2 x 10 mol per mol of silver Coupler EX-2...0.02 mol Coupler EX-5...silver for 1 mole
0.0016 mol 5th layer: Intermediate layer 6th layer same as the 2nd layer: Low green sensitivity emulsion layer Silver iodobromide emulsion (silver iodide; 4 mol %)...Amount of coated silver
1.2g/ ^m2 Sensitizing dye...3 x 10 mol per mol of silver Sensitizing dye...1 x 10 mol per mol of silver Coupler EX-4...0.05 mol Coupler EX-8...silver 0.008 mole for 1 mole coupler EX-6...for 1 mole of silver
0.0015 mol 7th layer: Highly sensitive green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol%)...Amount of coated silver
1.3g/m ² Sensitizing dye...2.5 x 10 mol per mol of silver Sensitizing dye... 0.8 x 10 mol coupler EX-3...0.017 mol coupler EX-3 per mol silver...Silver 1 0.003 mol per mole 8th layer; Yellow filter layer Yellow colloidal silver and 2,5 mol in gelatin aqueous solution
- gelatin layer 9th layer containing an emulsified dispersion of di-t-octylhydroquinone; low-sensitivity blue-sensitivity emulsion layer silver iodobromide emulsion (silver iodide; 6 mol %)...Amount of coated silver
0.7 g/m ² Coupler EX-9...0.38 mol per mol of silver Coupler EX-6...0.015 mol per mol of silver 10th layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide (silver iodide; 6 mol%)...Amount of coated silver
0.6g/m ² Coupler EX-9...1.0 mol per mol of silver 11th layer; First protective layer silver iodobromide (silver iodide 1 mol%, average grain size 0.07μ)
…Amount of coated silver 0.5g 12th gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-1; 2nd protective layer Trimethylmethanoacrylate particles (diameter approx.
Apply a gelatin layer containing 1.5μ). In addition to the above composition, each layer contains a gelatin hardening agent H.
-1 and a surfactant were added. The sample prepared as described above was designated as sample 101. Compound sensitizing dye used to prepare the sample: anhydro-5,5'-dichloro-
3,3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye: anhydro-9-ethyl-3,3'-
Di-(γ-sulfopropyl)-4,5,4'-5'-
Dibenzothiacarbocyanine hydroxide
Triethylamine salt sensitizing dye: anhydro-9-ethyl-5,5'-
Dichloro-3,3'-di-(γ-sulfopropyl)
Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di-
{β-[β-(γ-sulfopropyl)ethoxy]
Ethylimidazolocarbocyanine hydroxide sodium salt The development used here was carried out at 38°C as described below. 1 Color development... 3 minutes 15 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing... 3 minutes 15 seconds 6 Stability... 3 minutes 15 seconds The composition of the treatment liquid 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-β-hydroxyethylamino)-2-methylaniline sulfate Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Ammonia water (28%) 25.0cc Ethylenediamine-tetraacetic acid sodium iron salt
130.0g Glacial acetic acid 14.0cc Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0cc Sodium bisulfite 4.6g Add water 1 Stabilizer formalin 8.0cc Add water 1 Preparation of Samples 102 to 107 The coupler EX-6 of the low green sensitivity layer of Sample 101 is shown in Table 1.
It was prepared in the same manner as Sample 101 except that the coupler was changed to the one shown in . When Samples 101 to 107 were wedge-exposed to white light and processed, magenta images with almost the same sensitivity and gradation were obtained. The MTF values of magenta color images of these samples were measured. Regarding MTF values, see “The
Theory of the Photographic Process” 4th edition
It is stated on P604. The results are shown in Table 1. Comparative compound A (compound-2 described in JP-A-57-111536)

[Table] As is clear from Table 1, the coupler of the present invention is
It is possible to provide a photosensitive material with exactly the same sensitivity and particularly excellent sharpness. Example 2 Samples 202 to 206 In sample 101 produced in Example 1, the ninth layer,
Samples except that 1/2 mole of EX-9 was added to the compound shown in Table 2 in place of the coupler EX-9 in the 10th layer.
Samples 202 to 205 were prepared in the same manner as 101. Sample 206
was prepared in the same manner using the same molar amount of Comparative Compound B in place of EX-9. When the obtained samples 101 to 205 were wedge exposed to white light and processed, yellow images with almost the same sensitivity and gradation were obtained. Additionally, conventional RMS values were determined for the yellow color images of these samples. Determination of graininess by RMS method is "Photographic Science and Engineering"
Described in Vol. 19; No. 4 (1975) P235. Table 2 shows the RMS values at fog density +0.2. Samples 202 to 205 containing the compounds of the present invention had better granularity than sample 101. Furthermore, when the film thickness was measured, all of the samples of the present invention were found to be thinner than sample 101.

[Table] Comparative compound B (compound-2 described in JP-A-57-111537) As described above, the coupler having the structure of the present invention can provide a light-sensitive material having excellent performance in terms of graininess and sharpness. The compounds of the present invention can be prepared by conventional methods of adding couplers to emulsions or dispersing them, and adding them to gelatin/silver halide emulsions or hydrophilic colloids. For example, high boiling organic solvents - dibutyl phthalate, tricresyl phosphate,
A method of mixing and dispersing wax, higher fatty acids and their esters with a coupler, for example, US Patent No.
The method described in No. 2304939, No. 2322027, etc. Also, a method in which a low boiling point organic solvent mixes and disperses a water-soluble organic solvent and a coupler. A method of dispersing couplers in combination with a high boiling point organic solvent. For example, U.S. Patent Nos. 2801170, 2801171,
The method described in issue 2949360 etc. A method of dispersing the coupler alone or in combination with other couplers, such as colored couplers or uncolored couplers, when the coupler itself has a sufficiently low melting point (for example, 75°C or lower). For example, the description in German Patent No. 1143707 is applicable. Dispersion aids include commonly used anionic surfactants (e.g. sodium alkylbenzene sulfonate, sodium di-octyl sulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate, Fischer type couplers, etc.), amphoteric Surfactants (e.g. N
-tetradecyl/N/N dipolyethylene alpha betaine, etc.) and nonionic surfactants (eg, sorbitan, monolaurate, etc.) are used. Couplers used in combination with the compound of the present invention include, for example, the following known couplers. A specific example of a magenta coloring coupler is a U.S. patent
No. 2600788, No. 2983608, No. 3062653, No.
No. 3127269, No. 3311476, No. 3419391, No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558319, No. 3582322, No.
No. 3615506, No. 3834908, No. 3891445, No. 3891445, No. 3834908, No. 3891445, No.
No. 4367282, No. 4366237, No. 4351897, No. 4367282, No. 4366237, No. 4351897, No.
No. 4338393, No. 4241168, West German Patent No. 1810464,
West German patent application (OLS) No. 2408665, OLS No. 2417945,
No. 2418959, No. 2424467, Special Publication No. 40-6031,
JP-A No. 51-20826, No. 52-58922, No. 49-
No. 129538, No. 49-74027, No. 50-159336, No.
No. 52-42121, No. 49-74028, No. 50-60233,
These are those described in No. 51-26541, No. 53-55122, etc. A specific example of a yellow coupler is a U.S. patent.
No. 2875057, No. 3265506, No. 3408194, No.
No. 3551155, No. 3582322, No. 3725072, No.
No. 4356258, No. 3891445, West German Patent No. 1547868,
West German Application No. 2219917, West German Application No. 2261361, West German Publication No.
No. 2414006, British Patent No. 1425020, Special Publication No. 1977-
No. 10783, JP-A-47-26133, JP-A No. 48-73147,
No. 51-102636, No. 50-6341, No. 50-123342
No. 50-130442, No. 51-21827, No. 50-
It is described in No. 87650, No. 52-82424, No. 52-115219, etc. Specific examples of cyan couplers are U.S. Patent No. 2369929,
4362810, 4368257, 4341864, 4362810, 4368257, 4341864,
No. 4333999, No. 4342825, No. 4345025, No. 4342825, No. 4345025, No.
No. 2434272, No. 2474293, No. 2521908, No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
3591383, 3767411, 4004929, West German Patent Application (OLS) 2414830, 2424329, JP 48-59838, 51-26034, 48-5055,
These are those described in No. 51-146828, No. 52-69624, and No. 52-90932. As a colored coupler, for example, a US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, JP-A No. 51-26034, No. 52-
Specification No. 42121, West German Patent Application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 4355100, No. 3227554, No. 3617291, No. 4355100, No.
No. 4248962, No. 3701783, No. 3790384, No.
No. 3632345, West German Patent Application (OLS) No. 2414006,
No. 2454301, No. 2454329, No. 3209486, British Patent No. 953454, Japanese Unexamined Patent Publication No. 1986-69624, No. 49-
Those described in No. 122335 and Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, U.S. Pat.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
Those described in No. 15271 and JP-A-53-9116 can be used. High boiling point organic solvents include, for example, US Pat. No. 2,322,027;
No. 2533514, No. 2835579, Special Publication No. 1972-23233,
US Patent No. 3287134, British Patent No. 958441, JP-A-Sho
No. 47-1031, UK Patent No. 1222753, US Patent
No. 3936303, Japanese Patent Application Publication No. 1983-26037, Japanese Patent Application Publication No. 1973-
82078, U.S. Patent No. 2353262, U.S. Patent No. 2852383, U.S. Pat.
No. 3554755, No. 3676137, No. 3676142, No. 3676142, No. 3676137, No. 3676142, No.
No. 3700454, No. 3748141, No. 3837863,
OLS2538889, JP-A-51-27921, JP-A No. 51-
No. 27922, No. 51-26035, No. 51-26036, No. 50
-62632, Special Publication No. 49-29461, US Patent
It is described in No. 3936303, No. 3748141, and Japanese Patent Application Laid-open No. 1521/1983. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. In addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Fapan.No.16, 30 are used as gelatin.
(1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. In the photographic emulsion used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide. The average grain size of silver halide grains in photographic emulsions (spherical or near-spherical grains, regular grains such as cubes and octahedrons, tabular grains, etc.) is based on the volume average equivalent to a sphere. The particle size (particle size) is preferably 5μ or less, particularly preferably 3μ or less. The particle size distribution may be narrow or wide. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubic or octahedral, or may have irregular crystal shapes such as spherical or plate-like. It may also have a composite crystalline form. It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase. According to this method, a silver halide emulsion with 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 present. Silver halide emulsions are usually chemically sensitized. For chemical sensitization, see, for example, H. Frieser, ed., Die
Grundlagen der photographischen Prozesse
mit silberhalogeniden (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. Namely, 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, Reduction sensitization using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds; noble metal compounds (e.g., gold complex salts, Pt,
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. i.e. azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenz Imidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazoline thione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,
7) Many compounds known as antifoggants or stabilizers can be added, such as tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; etc. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsion dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast Various surfactants may be included for various purposes such as sensitization, sensitization), etc. For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion layer of the photographic light-sensitive material prepared using the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, and thiomorpholins. , quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure No. 176, pages 28-30 (RD
-17643), any of the known methods and known treatment liquids can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. Processing temperature is usually 18℃ to 50℃
Selected between 18℃ or lower temperature than 50℃
The temperature may exceed ℃. The developer used in black-and-white photographic processing can contain known developing agents. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. may be used alone or in combination. It can be used as The developing solution generally contains other well-known preservatives, alkaline agents, PH buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like. When forming a dye image, conventional methods can be applied.
For example, negative-positive method (e.g. “Journal of the
Society of Motion Picture and Television
Engineers, Vol. 61 (1953), pp. 667-701); developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other A color reversal method in which a dye-positive image is obtained by performing appropriate fogging treatment and subsequent color development; a photographic emulsion layer containing a dye is exposed and developed to form a silver image, and this is used as a bleaching catalyst to bleach the dye. Silver dye bleaching method etc. are used.The color developer generally consists of an alkaline aqueous solution containing a color developing agent.The color developing agent is a known primary aromatic amine developer such as phenylenediamines (e.g. 4-amino-N , N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-methyl-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. The color developer may also contain a PH buffer, a development inhibitor or an antifoggant. In addition, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity-imparting agents, polycarboxylic acid chelating agents, and antioxidants are added as necessary. It may also include. Specific examples of these additives include Research Disclosure (RD-17643) and U.S. Patent No. 4083723.
No., OLS No. 2622950, etc. 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. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. Useful sensitizing dyes include, for example, German Patent No. 929080;
U.S. Patent No. 2493748, U.S. Patent No. 2503776, U.S. Patent No. 2519001,
No. 3912329, No. 3656959, No. 3672897, No. 3672897, No.
No. 4025349, British Patent No. 1242588, Special Publication No. 1977-
It is described in No. 14030. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. 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 necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In the photosensitive material produced using the present invention,
The photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. The photographic light-sensitive material produced using the present invention may contain an inorganic or organic hardening agent 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.) ), activated vinyl compound (1,
3,5-Triacryloyl-hexahydro-s-
triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4
-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, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the food 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. 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, sialin dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

Claims (1)

[Scope of Claims] 1. A silver halide color light-sensitive material characterized by having a coupler represented by the following general formula on a support. General formula A-X-B-Y In the formula, A and B each represent a coupler component, X is bonded to coupler component A at the position where coupler component A couples with the oxidized developing agent, and coupler component B is Coupler component B at a position other than the position where it couples with the oxidized developing agent
Y represents an atomic group, a hydrogen atom, or a halogen atom that bonds to coupler component B at the position where coupler component B couples with the oxidized developing agent.