JPH0750318B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material excellent in sharpness.

(Prior Art) By color-developing a silver halide color photographic material, an oxidized aromatic primary amine color developing agent and a coupler react to react with indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is known that similar dyes are formed and color images are formed.

In this method, the subtractive color method is usually used for color reproduction.
A silver halide emulsion selectively sensitive to blue, green, and red and a yellow, magenta, and cyan color image forming agent (coupler) having a complementary color relationship with each other are used.

A number of studies have been conducted in the past for improving the performance of color formers (couplers) for forming image dyes, and many have been disclosed in patents and technical literature. These are used for color photographic materials as described above. The performance of couplers that are used has a great influence on overall photographic performance, such as image quality performance such as sensitivity, color reproducibility, sharpness, or graininess, and color image storage performance against heat, light, or humidity. Because nothing else. For example, when the coupler has a coupling reaction with an oxidized product of a developing agent, the spectral absorption width of the dye formed is broad or there is an unwanted side absorption, which causes color turbidity and impairs color reproducibility. Also, the larger the amount of dye that can be produced from the coupler per unit weight, the smaller the amount of coupler that can be added to the emulsion layer, and as a result, the emulsion film thickness is reduced and the color bleeding phenomenon caused by optical factors is suppressed, resulting in a sharp image. The degree is improved. Further, the higher the stability of the dye formed by the coupler with respect to heat, light, humidity, or the material components contained in the color photograph, the better the storage stability of the image dye. Further, the higher the coupling reaction rate of the coupler with the oxidized product of the developing agent, the more efficiently the development takes place and the higher the sensitivity of the light-sensitive material.

For example, the following are known as specific examples of the couplers proposed for improving the photographic performance as described above.

Journal of Chemical Society, Perkin I, 1977, 2047
The page reports a coupler in which the azomethine dye produced from a 5-pyrazolone type coupler has a small side absorption on the short wavelength side. U.S. Pat. No. 4,248,961 discloses a bis-type yellow coupler for the purpose of reducing the molecular weight of the coupler required to form a fixed amount of dye concentration. Also, U.S. Pat.Nos. 3,311,476 and 4,1
No. 24,396 proposes a coupler with improved color image fastness. Also, U.S. Pat.Nos. 4,296,199 and 4,301,235
U.S. Pat. No. 5,837,069 discloses a coupler having a high color forming property, which is advantageous for increasing the sensitivity. Thus, in recent years, progress in performance has been observed in the molecular design of couplers, but it is not always sufficient, and rather, because of the inevitable constraints that occur as long as conventional couplers are used,
It can be said that it is difficult to further improve the performance. The inevitable constraint that the conventional coupler has is that the coupler itself "receives the image information accumulated in the silver halide via the oxidized form of the developing agent,
It has the function of "becoming the chromophore component of the image dye itself". For this reason, the properties of the image dye formed are determined by the molecular structure of the coupler, causing various contradictions in molecular design. For example, even if a coupler with a high coupling rate is molecularly designed, the resulting image dye has a spectral absorption in an undesired wavelength range or a large secondary absorption.
Even in the case of a coupler that produces a robust dye, if the coupling speed is small, or if the coupler has a spectral absorption width that forms a dye without side absorption, there is a problem in the stability of the coupler. It can be mentioned as an example. That is, the guideline for selecting a coupler for achieving an efficient color forming function and the guideline for selecting a coupler for achieving a desired function as an image dye are not necessarily compatible with each other. Under such circumstances, JP-A-54-145135 discloses a dye release timing coupler.

The method of the patent utilizes the hue of the anion structure of the hydroxy-substituted aromatic azo dye produced by the development processing. By the way, after the completion of the usual development processing, since the pH of the film is weakly acidic, the azo dye released by the coupling reaction with the oxidation product of the aromatic primary amine developing agent is partly The color is erased by the protocol, resulting in a decrease in image density. Alternatively, since the counter cation of the azo dye is a metal ion in the developer, it is difficult to say that the image storability is sufficient. In order to solve these problems, the patent proposes that a high pH (about 11.0) stabilizing bath containing bromide in cetyltrimethylammonium is used as the final bath in order to retain the hue of the azo dye produced. It can be said that there is a problem in practical use because it requires various treatments.

(Problems to be Solved by the Invention) Accordingly, the first object of the present invention is to provide a color photographic light-sensitive material capable of obtaining excellent sharpness.

The second object of the present invention is to provide a color photographic light-sensitive material excellent in image fastness.

A third object of the present invention is to provide a silver photographic color photographic light-sensitive material.

(Means for Solving Problems) The above object was achieved by a silver halide color photographic light-sensitive material containing a compound represented by the following general formula (IA).

General formula (IA) However, A is the general formula (IB) Represents

In the above formula, L ₁ represents —SO ₂ L ₁₀ or —C (L ₁₁ ) ₃ . L ₁₀ represents an aliphatic group, an aromatic group, a heterocyclic group, or an amino group, each of which may be unsubstituted or may have a substituent, L 10
₁₁ represents a halogen atom. At least one of L ₂ and L ₃ represents an electron-withdrawing group. L ₄ , L ₅ , L ₆ , L ₇ , L ₈ , L ₉ ,
And L ₂ and L ₃ other than the case of representing an electron-withdrawing group are each independently a hydrogen atom, a halogen atom, an aliphatic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxy group, an aryloxy group, Represents a carbonamido group, a sulfonamide group, a ureido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, a cyano group, and a nitro group, and groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group are substituents. May have.

L ₃ and L ₄ , L ₈ and L ₉ , and L ₅ and L ₆ may be bonded to each other to form a 5-membered to 7-membered ring.

Time represents a timing group, and n represents an integer of 0 or more.

Cp represents a coupler residue that binds to Time _n at the coupling position. Time _n is a trivalent group, and Cp
May have a non-coupling position and / or a bond with PUG (bond represented by a dotted line in the general formula (IA)).

X is -O-, -S-, or And L ₁₂ represents a hydrogen atom, an aliphatic group, an aromatic group, or an acyl group.

In the general formula, (Time) represents a timing group, and n represents 0 or a positive integer. The timing group represented by Time when n ≧ 1 represents a divalent or trivalent organic group (when further having a bond with the non-coupling part of Cp) which bonds A to the coupling part of Cp. When n = 0, A is directly connected to the coupling part of Cp. Examples of the mechanism for releasing A when it has Time include those disclosed as a photographically useful group (hereinafter abbreviated as PUG) release timing coupler.

US Pat. No. 4,248,962, a method for releasing PUG by intramolecular nucleophilic substitution reaction after withdrawal, JP-A-56-114946,
57-154234, and a method for releasing PUG by electron transfer along the conjugated system after leaving, as described in JP-A-57-188035,
56837 and 56-209740, a method of releasing a PUG by causing an intramolecular nucleophilic substitution reaction by a nucleophilic group newly generated by electron transfer along a conjugated system after leaving, as described in Japanese Patent Application No.
9-75475 and 59-89719, the method of releasing PUG upon cleavage of hemiacetal after withdrawal and the like can be mentioned. As the timing group in the present invention, all the leaving groups in the above photographic coupler can be used. In addition to this, JP-A-58
No. 209740, Cp and Time also have a bond at the non-coupling site of Cp, and Cp and Time even after the coupling reaction with the oxidized developing agent and the subsequent reaction.
And may have a bond. In addition, Japanese Patent Application No. 59-89719,
As described in U.S. Pat. Nos. 59-90437, 59-92556 and 59-92557, Time and PUG further form a bond that does not cleave even after a coupling reaction with an oxidized form of a developing agent and a subsequent reaction. They may be included, but these systems are also included.

In each of the above cases, the present invention may further have a bond between Cp and A which is not cleaved after the coupling reaction with the oxidized developing agent and the subsequent reaction. Alternatively, the structure of the general formula [IA] may further have such a bond which is not cleaved between Cp and Time and between Time and A. Examples of the auxiliary chromophore hetero atom represented by X include a nitrogen atom, an oxygen atom, and a sulfur atom, and preferably an oxygen atom.

The group represented by the general formula [IB] is an azo dye residue,
By blocking the auxochrome group by Cp or (Time), the maximum absorption wavelength is shifted to the short wavelength side, and the maximum absorption wavelength before the shift is changed by the reaction with the oxidized product of the developing agent. It is the main constituent of the dye.
More preferably, the auxiliary chromophore has an appropriate hue in a dissociated state.

Next, the substituent L in the general formula [IB] is described in detail.

In the general formula (IB), L ₁ is --SO ₂ L ₁₀ or --C (L ₁₁ ) ₃
Represents L ₁₀ represents an aliphatic group, an aromatic group, an amino group or a heterocyclic group, and L ₁₁ represents a halogen atom.

When L ₁₀ represents an aliphatic group, it preferably has 1 to 22 carbon atoms.
May be substituted or unsubstituted, chain-like or cyclic. A preferred substituent of the aliphatic group is an alkoxy group,
An aryloxy group, an amino group, an acylamino group, a halogen atom and the like, which may themselves have a substituent.

Specific examples of aliphatic groups useful as L ₁₀ are: methyl, ethyl, isopropyl, isobutyl, 1,1-dimethylhexyl, dodecyl, hexyl, hexadecyl, 2-methoxyisopropyl, trichloromethyl. , Chloromethyl, dichloromethyl, trifluoromethyl, benzyl, cyclopentyl, cyclohexyl, 2
-Decenyl, 4-ethoxybenzyl, allyl, phenylethyl and the like. L ₁₀ is an aromatic group (especially a phenyl group)
When represented, the aromatic group may be substituted. An aromatic group such as a phenyl group is an alkyl group having 22 or less carbon atoms,
Alkenyl group, alkoxycarbonyl group, alkoxycarbonylamino group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, sulfonyl group, hydroxyl group, carboxy group,
It may be substituted with a nitro group, a cyano group, a halogen atom or the like. Specific examples of the aromatic group include phenyl, tolyl, 4-methoxyphenyl, 4-chlorophenyl and the like.

When L ₁₀ represents an amino group, it preferably has 1 to 20 carbon atoms.
Which is an aliphatic amino group or an anilino group, and the aliphatic group and the phenyl group may have a substituent defined when L ₁₀ has an aromatic group. Specific examples include a dimethylamino group, a 2-methoxyethylamino group,
Examples thereof include a methylamino group, an ethylamino group, an anilino group, a 4-cyano-anilino group, and a morpholino group.

When L ₁₀ represents a heterocyclic group, preferable heterocycles include a pyridyl group, a furanyl group, a piperidyl group, a benzthiazolyl group, a pyrazolyl group, a pyridyl group and an imidazolyl group. Further, the ring may have a substituent similar to that shown for the aromatic group.

In the general formula [IB], at least one of L ₂ and L ₃ represents an electron-withdrawing group, and is preferably a halogen atom, a trihalomethyl group, a sulfonyl group, a sulfinyl group, a nitro group, a cyano group, an acyl group. Group, an alkoxycarbonyl group, and a quaternary ammonium salt.

More preferably, it represents a halogen atom, a trifluoromethyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a cyano group or a nitro group. In this case, the alkyl or aryl group may further have a substituent. In particular,
Examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a chloro atom, a fluorine atom, a phenylsulfonyl group, a 4-chlorophenylsulfonyl group, a phenylphenyl group, an ethylsulfinyl group and a phenylsulfinyl group.

L _{4 to} L ₉ and L ₂ and L other than when representing an electron-withdrawing group
₃ is a hydrogen atom, a halogen atom, an aliphatic group, an acyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, alkoxy group, aryloxy group, carbonamido group, sulfonamide group, ureido group, carbamoyl group,
Sulfonyl group, sulfinyl group, cyano group, nitro group,
Represents a sulfamoyl group. When L _{2 to} L ₉ represent an acyl group, they preferably have 2 to 16 carbon atoms, and examples thereof include acetyl and decanoyl groups. When L _{2 to} L ₉ represent an alkoxycarbonyl group, it is preferably an alkyl residue having 1 to 32 carbon atoms, for example,
Methoxycarbonyl, butoxycarbonyl, octoxycarbonyl, dodecyloxycarbonyl, 2-methoxyethoxycarbonyl and the like can be mentioned. When L _{2 to} L ₉ represent an aryloxycarbonyl group, they preferably have 6 to 20 carbon atoms, and examples thereof include a phenoxycarbonyl group and a tolyloxycarbonyl group. When L _{2 to} L ₉ represent a sulfonyl group, it preferably has 1 to 20 carbon atoms, and examples thereof include methylsulfonyl, ethylsulfonyl, propylsulfonyl, octylsulfonyl, trichloromethylsulfonyl, trifluoromethylsulfonyl, and phenoxy. Examples thereof include sulfonyl, 4-methoxyphenylsulfonyl, and the like.

The alkyl or allyl group of the sulfonyl group may have a substituent specified when L ₁₀ represents an aromatic group.

When L _{2 to} L ₉ represent a sulfamoyl group, it preferably has 1 to 32 carbon atoms, and examples thereof include dimethylsulfamoyl, diethylsulfamoyl, octylsulfamoyl, methyl, octadecylsulfamoyl and phenyls. Examples thereof include rufuamoyl and 2,4-di-t-pentylphenylsulfamoyl.

When L _{2 to} L ₉ represent a ureido group, examples thereof include methylureido and phenylureido.

When L _{2 to} L ₉ represent a sulfonamide group, they preferably have 1 to 20 carbon atoms, and examples thereof include methanesulfonamide, toluenesulfonamide, and hexadecanesulfonamide.

When L _{2 to} L ₉ represent a carbamoyl group, it preferably has 2 to 32 carbon atoms, such as ethylcarbamoyl,
Octylcarbamoyl, 2,4-di-t-pentylphenylcarbamoyl and the like can be mentioned.

When L _{2 to} L ₉ represent a sulfinyl group, it preferably has 1 to 32 carbon atoms, and examples thereof include methylsulfinyl, ethylsulfinyl, propylsulfinyl, octylsulfinyl and trichloromethylsulfinyl. And nil, trifluoromethylsulfinyl, phenylsulfinyl, 4-methoxyphenylsulfinyl, and the like. The alkyl group and aryl group of this sulfinyl group may have a substituent specified when L ₁₀ represents an aromatic group.

When L _{2 to} L ₉ represent an alkoxy group, they preferably have 1 to 32 carbon atoms and may have a substituent on the alkyl group. In that case, the substituent is selected from the substituents defined when L ₁₀ represents an aromatic group.

For example, methoxy, ethoxy, 2-methoxyethoxy, octyloxy and the like can be mentioned.

When L _{2 to} L ₉ represent an aryloxy group, it preferably has 6 to 20 carbon atoms, particularly preferably a phenyloxy group, and is defined when L ₁₀ represents an aromatic group on the aromatic ring. It may have a substituent. For example, a phenoxy group, a 4-cyanophenoxy group, a 4-methoxyphenoxy group and the like can be mentioned.

When L _{2 to} L ₉ represent a carbonamido group, preferably
It has 1 to 32 carbon atoms, and examples thereof include acetamide, benzamide, and (2,4-di-tert-amylphenoxy) acetamide group.

When L _{2 to} L ₉ represent an aliphatic group, preferably they have 1 to 1 carbon atoms.
22 may be substituted or unsubstituted, linear or cyclic. Preferred substituents of the aliphatic group are an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom and the like, which may themselves have a substituent.

A specific example of an aliphatic group useful as L _{2 to} L ₉ is methyl,
Ethyl, isopropyl, dodecyl, hexyl, chloromethyl, 2-methoxymethyl, trifluoromethyl, 4-
Ethoxybenzyl, and the like.

In the general formula (IA), it may be a bis type coupler or a polymer coupler in which two or more molecules are linked at the Cp, Time _n or A portion.

Further, the present invention is particularly effective in that the compound represented by the general formula (I
In A), Cp is represented by the following general formulas (II), (III), (IV),
(V), (VI), (VII), (VIII), (IX),
When it is a coupler residue represented by (X), (XI) or (XII). These couplers are preferred because of their high coupling speed.

General formula (II) General formula (III) General formula (IV) General formula (V) General formula (VI) General formula (VII) General formula (VIII) General formula (IX) General formula (X) General formula (XI) General formula (XII) The free bond derived from the coupling position in the above formula represents the coupling position of the coupling-off group. In the above formula, when R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ or R ₁₁ contains a diffusion resistant group, it has a total number of carbon atoms. It is selected to be 8 to 32, preferably 10 to 22, and otherwise the total number of carbon atoms is preferably 15 or less.

Next, R _{1 to} R ₁₁ , l, m and p in the general formulas (II) to (XII) will be described.

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

When R ₁ , R ₂ or R ₃ represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups are alkyl groups having a carbon number of 32 or less, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, fatty acid amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, alkylureido groups, It may be substituted with an alkyl-substituted succinimide group or the like, in which case the alkyl group may have an aromatic group such as phenylene interposed in the chain. The aromatic group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc. The moiety of the group may be further substituted with one or more alkyl groups having 1 to 22 total carbon atoms.

The aromatic group represented by R ₁ , R ₂ or R ₃ further includes an amino group substituted by 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 condensed with another ring, for example, a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group and the like. These substituents may themselves have a substituent.

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

When R ₁ , R ₂ or R ₃ represents a heterocyclic group, the heterocyclic group may be a carbon atom of a carbonyl group of an acyl group in an alpha acylacetamide or an amide group of an acyl group in one of the carbon atoms forming the ring. Combines with the nitrogen atom. Examples of such a heterocycle include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine,
Examples are pyritadine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, oxazine and the like. These may further have a substituent on the ring.

In the general formula [IV], R ₅ is a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (eg, methyl, isopropyl, tert-butyl, hexyl, dodecyl group, etc.), alkenyl group (eg, Allyl group), cyclic alkyl group (eg cyclopentyl group, cyclohexyl group, norbornyl group), aralkyl group (eg benzyl, β-phenylethyl group etc.), cyclic alkenyl group (eg cyclopentenyl, cyclohexenyl group etc.)
Represents a halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group. , Carbamoyl group, 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 , An anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group, hydroxy group, mercapto group and the like.

Further, R ₅ may represent an aryl group (eg, phenyl group, α- to β-naphthyl group, etc.). The aryl group may have one or more substituents, and examples of the substituent include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group,
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 , A 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 hydronashi group, a mercapto group and the like. 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., which is exposed to light or heat of the coupler remaining in the film film. It is useful because it has few colors.

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

In the formula, R ₄ is a hydrogen atom and has 1 to 32 carbon atoms, preferably 1 to 32 carbon atoms.
22 straight chain or branched chain alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (these groups may have the substituents enumerated for R ₅ ), aryl groups and heterocyclic groups (these are It may have a substituent enumerated for R ₅ ), an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, naphthoxy). Carbonyl group), aralkyloxycarbonyl group (eg benzyloxycarbonyl group), alkoxy group (eg methoxy group, ethoxy group, heptadecyloxy group etc.), aryloxy group (eg phenoxy group, tolyloxy group etc.), alkylthio group (For example, ethylthio group, Silthio group etc.), arylthio group (eg phenylthio group, α-naphthylthio group etc.), carboxy group, acylamino group (eg acetylamino group, 3-[(2,4-di-tert-amylphenoxy) acetamido] benzamide group etc.) , Diacylamino group, N-alkylacylamino group (eg N-methylpropionamide group), N-arylacylamino group (eg N-phenylacetamide group), ureido group (eg ureido, N-aryl) Ureido, N-alkylureido group, etc.), urethane group, thiourethane group,
Arylamino group (for example, phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-5-tetradecanamidoanilino group, etc.), alkylamino group (for example, n-butylamino group, methylamino group) , Cyclohexylamino group, etc.),
Cycloamino group (for example, piperidino group, pyrrolidino group, etc.), heterocyclic amino group (for example, 4-pyridylamino group,
2-benzoxazolylamino group etc.), alkylcarbonyl group (eg methylcarbonyl group etc.), arylcarbonyl group (eg phenylcarbonyl group etc.), sulfonamide group (eg alkylsulfonamide group, arylsulfonamide group etc.) A carbamoyl group (eg, ethylcarbamoyl group, dimethylcarbamoyl group, N
-Methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (for example, 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 sulfo group Represents

In the formula, R ₆ represents a hydrogen atom or a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, and these are as described above. It may have the substituents listed for R ₅ .

R ₆ may represent an aryl group or a heterocyclic group, and these may have the substituents enumerated above for R ₅ . ) Further, 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,
Sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group , N
-Arylanilino group, N-alkylanilino group, N-
It may 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 usual 4-equivalent phenol or α-naphthol coupler, and specifically, R ₇ is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group or an aliphatic carbon group. Hydrogen residue, N
—Arylureido group, acylamino group, —O—R ₁₂ or —S—R ₁₂ (provided that R ₁₂ is an aliphatic hydrocarbon residue), and when two or more R ₇ are present in the same molecule, Is 2
One or more R ₇ may be different groups, and the aliphatic hydrocarbon residue includes one having a substituent.

Further, when these substituents include an aryl group, the aryl group may have the substituents enumerated above for R ₅ .

Examples of R ₈ and R ₉ include an aliphatic hydrocarbon residue, a group selected from an aryl group and a heterocyclic residue,
Alternatively, one of these may be a hydrogen atom and includes those having a substituent in these groups, and R ₈ and
R ₉ may together form a nitrogen-containing heterocyclic nucleus.

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

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

R ₁₀ is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent, and examples of the substituent include an alkoxy group, an alkoxycarbonyl group, an acylamino group,
Examples thereof include an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsuccinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group or an aryl group.

R ₁₁ represents an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Alkoxycarbonyl group or aryloxycarbonyl group with 1 carbon
To 32, preferably 1 to 22 alkanesulfonyl group, arylsulfonyl group, aryl group, 5-membered or 6-membered heterocyclic group (as a hetero atom, selected from nitrogen atom, oxygen atom and sulfur atom, for example, triazolyl group, imidazolyl group , A phthalimido group, a succinimido group, a furyl group, a pyridyl group or a benzotriazolyl group), each of which may have the substituent described in the above R ₁₀ .

The coupler represented by formula (IA) of the present invention includes a case where it is a polymer. That is, it is derived from a monomer coupler represented by the following general formula (XIII),
A polymer having a repeating unit represented by V) or a non-color-forming monomer containing at least one ethylene group which has no ability to couple with an oxidation product of an aromatic primary amine developing agent. It is a copolymer with one or more species.
Here, two or more monomer couplers may be polymerized at the same time.

General formula (XIII) General formula (XIV) In the formula, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms,
Or represents a chlorine atom, A ₁ is -CONH-, -NHCONH-,
-NHCOO -, - COO -, - SO 2 -, - CO -, - NHCO -, - S
_{O 2 NH -, - NHSO 2} -, - OCO -, - OCONH -, - NH- or represents -O-, A ₂ represents -CONH- or -COO-, A
₃ represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group, and the alkylene group may be linear or branched.

(Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, arylene groups such as phenylene, naphthylene, etc.) Represents a compound residue represented by the general formula (IA),
It may be bound at any site of Cp, Time and A.

i, j, and k represent 0 or 1, but i, j,
And k cannot be 0 at the same time.

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

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

The addition layer of the coupler of the present invention is a photosensitive silver halide-containing layer or a layer adjacent thereto.

When the coupler is added to the light-sensitive silver halide-containing layer, it is added to 1 mol of silver halide contained in the layer, and when it is added to the adjacent layer, it is contained in the adjacent layer. 0.001 to 1 mol is preferable to 1 mol of silver halide. It is particularly preferably in the range of 0.005 to 0.5 mol.

In the compound represented by the general formula (IA) of the present invention, A
The group represented by is a dye residue, and the residue is represented by the general formula (IB). In formula (IB), X is an auxochrome heteroatoms dye residue, by A is bonded through CPTIME _n and X, spectral absorption wavelength dye residue had originally short Shift to the wavelength side.

At the time of development, the compound of the present invention is required to have at least one bond cleaved by a reaction with an oxidized product of a developing agent. Specific examples of the reaction include a reaction in which a leaving group bonded to the coupling position is released as an anion by a coupling reaction.

In this case, it is possible to produce two dyes in total by the azomethine dye produced by the coupling reaction and the dye produced by the pre-shifted dye.
Here, both of the two dyes can be used for forming a color image, or the azomethine dye that is initially formed is made soluble in an alkali so as to flow out to the processing solution during development, or is not exposed. Using the coupler residue of
Only the dyes produced from the shifted dyes can be used for color image formation.

In the case of the dye represented by A, such "temporary shift" is carried out by blocking a hydroxyl group or an amino group which is an auxiliary chromophore. Since azo dyes can take three forms, hydrazone and anion type, which usually absorb long waves, and azo type, which absorbs short waves, shortening is achieved by fixing to tautomeric azo type by blocking group. . Examples of dyes that are shortened by a blocking group include, for example, U.S. Patent Nos. 4,234,672 and 4,310,612.
No., No. 3,579,334, No. 3,999,991, No. 3,994,731,
Alternatively, there are the compounds described in No. 3,230,085. In these examples, in a photographic element of the diffusion transfer method, the blocking group is cleaved by alkali hydrolysis during development.

In the present invention, the bond is cleaved by the reaction with the oxidized product of the developing agent, and as a result, an auxochrome is produced. The maximum spectral absorption wavelength of the dye shifts by 20 nm or more, preferably 40 nm or more, or the molar absorption coefficient changes by 2 times or more, preferably 3 times or more before and after the bond is cleaved by the reaction with the oxidized product of the developing agent. is necessary.

When the compounds of the invention are used as color image forming agents, they need not be completely colorless in the shifted dye state. Generally, if the wavelength is shifted by blocking the auxochrome, the molar extinction coefficient changes from a fraction to a few tens, which is convenient.

For example, the compound of the present invention can be added to the blue-sensitive emulsion layer as a yellow image forming agent and used. When the auxiliary dye of the yellow dye is blocked and shortened, the molar extinction coefficient also decreases, so the apparent desensitization (filter effect) of the photosensitive emulsion caused by light absorption by the shifted dye is ignored. I can do it. Further, the compound of the present invention can be used as a magenta or cyan image forming agent by adding it to the green-sensitive and red-sensitive emulsion layers, respectively. When a magenta or cyan dye is blocked in an auxiliary chromophore to shorten the wavelength, it is convenient because it has a function as a conventional color correction (masking) coupler as a yellow colored or magenta colored coupler, respectively. Generally, the colored coupler is used as a mixture with the coupler used only for forming a color image, but it can be used alone in the compound of the present invention. Because, in the case of a shifted dye, the molar extinction coefficient increases when the color is restored, so if the molar extinction coefficient ratio of the dye is exactly the same as the mixing ratio of a conventional colored coupler, another color image forming coupler is mixed. Because there is no need.

Hereinafter, specific synthesis examples of the compound represented by the general formula [I] of the present invention will be shown.

1) A solution of Compound 1 (100 g) and methanesulfonyl chloride (88 g) was added little by little to anhydrous aluminum chloride (1
05g) is added. The mixture is heated to reflux at an oil temperature of 130 ° C. for 3 hours. After cooling, the mixture is poured into ice water and extracted with ethyl acetate, and the organic layer is washed with water and dried. The organic layer was distilled off under reduced pressure and the obtained oily substance was crystallized from hexane / ethyl acetate to give 60 g of the desired compound 2 as colored crystals.

2) Thioglycolic acid (77 g) is dissolved in water (300 ml), and NaHCO ₃ (138 g) is gradually added therein. After the addition is complete, compound 2 (170 g) is added and the mixture is heated to reflux for 3 hours. After cooling, it is further diluted with water and washed with ether. The aqueous layer is acidified with hydrochloric acid and extracted with ethyl acetate. The organic layer is washed with water, dried and evaporated under reduced pressure to give an oily substance. Crystallization with ether gave 124 g of the desired compound 3 as a single product.

3) Compound 3 (123 g) was dissolved in anhydrous DMSO (50 ml),
A methanol solution (170 g) containing CH ₃ ONa (48 g) in it
g) is added dropwise.

The mixture is heated at an oil temperature of 80 to 90 ° C. for 1 hour, cooled, poured into water, washed with ether, and then acidified with hydrochloric acid.

The aqueous layer is extracted with ethyl acetate, washed with water, and the organic layer is dried with Na ₂ SO ₄ . The organic layer is evaporated under reduced pressure to give an oily substance. Crystallization of the oily substance with ether / ethyl acetate / hexane gives the desired compound 4 as (79 g) white crystals.

4) Compound 4 (79g) was dissolved in acetic acid (350ml) to give 33%
H ₂ O ₂ (147 g) is added slowly. Reflux the mixture for 3 hours,
Then cool. Dimethyl sulfide (20 ml) was added to the reaction mixture and stirred for 1 hour at room temperature. Confirm the absence of peroxide with KI / starch paper and distill off acetic acid and excess dimethyl sulphide under reduced pressure. The residual oily substance was crystallized from ethyl acetate / hexane to give the desired compound 4 (74 g) as white crystals.

Compound 5 (74g) in an aqueous solution (300ml) of NaOH (9.6g)
Get rid of. The mixture was heated under reflux for 2.5 hours, cooled, and the precipitated crystals were collected, washed with water, and dried to obtain 51 g of the desired compound 5. Compound 5 (39g) in anhydrous CH
Cool in a mixture of Cl ₃ (500 ml). 10 BBr ₃ (42 ml)
Dissolve in 0 ml CHCl ₃ and add carefully dropwise.

After dropping, remove the water bath and stir at an oil temperature of 40 to 50 ° C for 2 hours. After cooling, ice water was added to decompose excess BBr ₃ , and the crystals absorbed by perforation were collected, washed with water and dried to obtain 32 g of the desired compound 6. Compound 6 (30 g) was dissolved in methyl cellosolve (200 ml) and Et ₃ N (100 ml) was added to it to adjust the system temperature.
Stir while maintaining at 15 ° C. In it (Compound 7 (49
g), Na ₂ NO ₂ (10 g) and H ₂ SO ₄ (30 ml) were added little by little to the diazo form of compound 7 prepared in a mixed solvent of methyl cellosolve (650 ml) and water (20 ml). Keep the system temperature at 15 to 20 ℃ during dropping. After completion of dropping, the mixture is stirred at the same temperature for 1 hour, water is added, and the mixture is acidified with hydrochloric acid. The aqueous layer is extracted with ethyl acetate, the organic layer is washed with water and dried.

The organic layer was evaporated under reduced pressure, and the obtained oily substance was added to acetonitrile.
Crystallization with / EtOH and recrystallization with ethyl acetate / hexane were repeated to obtain 17 g of the target compound 8 as red crystals.

Compound 8 6.4 g and compound 9 5.5 g were dissolved in DMF 300 ml and K ₂ C was added.
Add 1.38 g of O ₃ and heat and stir at an oil temperature of 80 to 90 ° C. for 6 hours.

The reaction mixture is diluted with water, acidified with hydrochloric acid and extracted with ethyl acetate. The organic layer is washed with water and dried, and then the solvent is distilled off under reduced pressure to obtain 11.6 g of an oily substance. This oily substance was separated and purified by column chromatography (acetic acid: ethyl acetate: EtOH = 0.1: 10: 1) to obtain 6.1 g of the desired Y-2 as pale yellow crystals.

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

The above-mentioned shift width or change in molar extinction coefficient is also included when it is achieved as a result of being combined with other means.
The other means is, for example, a mordant for fixing the existing state of the azo dye to a hydrazo type and an anionic type, or a combined use with a basic dispersion medium.

As the compound having these functions, the following general formula (X
V) or (XVI) may be mentioned.

General formula (XV) General formula (XVI) In the formula, R ₂₁ represents an aliphatic group, an aryl group or a heterocyclic group, R ₂₂ , R ₂₃ or R ₂₄ represents a hydrogen atom, an aliphatic group or an aryl group, and R ₂₂ , R ₂₃ or R ₂₄ are mutually And / or R ₂₁ may be condensed and ring-closed. Further, the total sum of carbon atoms contained in the general formulas (XV) and (XVI) is 10 or more.

When R ₂₁ represents an aliphatic group, this aliphatic group has 1 carbon
~ 32 straight or branched chain alkyl group, aralkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group,
Represents an alkynyl group, which is a halogen atom (eg, chlorine atom, fluorine atom, etc.), an aryl group (eg, phenyl group, α- or β-naphthyl group, 2,4-dichlorophenyl group, 3-pentadecenyl group). Sylphenyl group, 2,4-
Di-t-amylphenyl group, etc.), heterocyclic group (for example, 2-pyridyl group, 2-benzothiazolyl group, 2-furyl group, N-piperidyl group, N-phthalimido group,
Etc.), cyano group, alkoxy group (eg, methoxy group,
Butoxy group, 2-ethylhexyloxy group, 2-methanesulfonylethoxy group, 3-phenoxypropoxy, etc.
Hexadecyloxy, etc.), aryloxy group (for example, phenoxy group, 4-chlorophenoxy group, 2,4-di-tert-butylphenoxy group, 3-methanesulfonamidephenoxy group, 4-cyanophenoxy group, 2-naphthoxy group, etc.), acylamino group (for example, acetamide group, benzamide group, (2,4-di-tert-amylphenoxy, acetamide group, 2- (2-chlorophenoxy))
Tetradecanamide group, 3- [2- (2,4-di-tert-
Amylphenoxy) butylamide] benzamide group,
Etc.), imide group (eg, succinimide group, phthalimido group, N-hydantoinyl group, etc.), anilino group (eg, phenylamino group, 2-chloroanilino group, N-
Methylanilino group, 2-chloro-5-tetradecanamidoanilino group, 4-methoxyanilino group, etc.), alkylamino group (for example, methylamino group, N, N-diethylamino group, N- (2-ethoxyethoxy)) Amino group,
Etc.), heterocyclic amino group (for example, 2-pyridylamino group, 2-imidazolylamino group, 2-pyrimidylamino group, etc.), ureido group (for example, methylureido group, N,
N-dipropylureido group, phenylureido group, 4-
Chlorophenylureido group, 4-propanesulfonylphenylureido group, etc.), sulfamoylamino group (for example, N, N-dimethylsulfamoylamino group, N-methyl-N-phenylsulfamoylamino group, N, N-diisopropylsulfamoylamino group, etc.), alkylthio group (eg, butylthio group, dodecylthio group, 3-
Phenoxypropylthio group, cyclopentylthio group, benzylthio group, etc.), arylthio group (for example, phenylthio group, 2-methylphenylthio group, 4-dodecylphenylthio group, 2-butyloxy-5-tert-octyl) Phenylthio group, 4-dodecyloxyphenylthio group,
Etc.), a heterocyclic thio group (for example, a 2-benzoxazolylthio group, a 1-ethyltetrazole-5-thio group, Etc.), an alkoxycarbonylamino group (for example, a methoxycarbonylamino group, a butoxycarbonylamino group,
Etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, dodecanesulfonamide group, 4-dodecyloxybenzenesulfonamide group) , Etc.), carbamoyl group (eg, N-methylcarbamoyl group, N, N-dibutylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, etc.), sulfamoyl group (eg, N -Butylsulfamoyl group, N-phenylsulfamoyl group, N, N-dipropylsulfamoyl group, N-methyl-N-phenylsulfamoyl group,
Etc.), a sulfonyl group (eg, methanesulfonyl group, dodecanesulfonyl group, benzenesulfonyl group, 4-toluenesulfonyl group, etc.), sulfinyl group (eg, methanesulfinyl group, benzenesulfinyl group, etc.),
Acyl group (eg, acetyl group, propanoyl group, dodecanoyl group, benzoyl group, pivaloyl group, 4-methoxybenzoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, tetradecyloxycarbonyl group, etc.), aryloxy A carbonyl group (eg,
Phenoxycarbonyl group, etc.), phosphonyl group (eg, methoxyphosphonyl group, butylphosphonyl group, phenylphosphonyl group, etc.), imino group (eg, propylideneimino group, etc.), cyanothio group, acyloxy group ( For example, acetoxy group, octanoyloxy group, benzoyloxy group, etc.), carbamoyloxy group (eg, N-acetylaminooxy group, N-benzoylaminooxy group, etc.), silyloxy group (eg, trimethylsilyloxy group, dibutyl) Methylsilyloxy group,
Etc.), sulfonyloxy group (eg, methanesulfonyloxy group, benzenesulfonyloxy group, etc.), heterocyclic oxy group (eg, 1-phenyltetrazole-5-
Oxy group, 2-tetrahydropyranyloxy group, etc.),
A hydroxy group and a nitro group may be substituted.

When R ₂₁ represents an aryl group, this aryl group represents an aryl group having 6 to 38 carbon atoms, and these are phenyl groups,
α-or β-naphthyl group, or the substituent or linear or branched chain alkyl group described in the aliphatic group of R ₂₁ ,
It represents an aryl group which may be substituted with an aralkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group or an alkynyl group.

When R ₂₁ represents a heterocyclic group, this ring may be saturated or unsaturated, contains at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom, and has the general formula [XV] or [ XVI], the atom bonded to the nitrogen atom is a nitrogen atom or a carbon atom, and the substituent or the straight chain, the branched chain alkyl group, the aralkyl group, the alkenyl group, the cyclo group described in the aliphatic group of R _21. It is a heterocyclic group which may be substituted with an alkyl group, a cycloalkenyl group or an alkynyl group.

In the general formula [XVI] and [XVII], Stated more detail R _22, R _23, and R _24, an aliphatic group of R _22, R _23, and R _24, aryl group, described in detail at the R ₂₁ And the same meanings as the aliphatic group and the aryl group.

In the general formula [XVI], E Represents an anion, eg
For example, halogen ions (for example, chloride ions, bromide ions)
On, iodide ion, etc.), sulfate ester ion (example
For example, methyl sulfate ion, ethyl sulfate ion, etc.)
Alkyl or aryl sulfonate ion (eg,
Tan sulfonate ion, ethane sulfonate ion, Ben
Zensulfonate ion, p-toluenesulfonate ion
Etc.), acetate ion, sulfate ion, and the like.
Among these, chloride ion, alkyl sulfate ion,
And arylsulfate are particularly preferred.

Further, the compound represented by the general formula [XV] or [XVI] is preferably added to the same or adjacent layer as the coupler-containing layer of the present invention, but may be added to a layer other than those depending on the purpose. Good.

The amount added is from 0.01 to 10 per mol of the coupler of the present invention.
It is 0 mol, preferably 0.1 to 10 mol.

Further, polymer compounds having the partial structures of the above general formulas [XV] and [XVI] in the molecule are also preferable.

These are what are referred to in the art as polymeric mordants and are polymers containing primary, secondary and tertiary amino groups,
Polymers having a nitrogen-containing heterocyclic moiety, polymers containing these quaternary cation groups, and the like have a molecular weight of 5,000 to 200,000, particularly 10,000 to 50,000.

For example, U.S. Pat.Nos. 2,548,568, 2,484,430, and 3,14
Vinyl pyridine polymers and vinyl pyridinium cation polymers disclosed in 8,061, 3,756,814 and the like; JP-A-55-48210, 55-129346, U.S. Patents 4,282,305, 4,273,853, 4,193,796. , The same 4,2
28,257, 4,229,515 and other imidazole-based polymers described in US Pat. Nos. 3,625,694,
3,859,096, 4,128,538, British Patent 1,277,
Polymer mordanting agents capable of cross-linking with gelatin etc. disclosed in US Pat. No. 3,958,995 and US Pat. No. 2,72.
1,852, 2,798,063, JP-A-54-115228, 54-
Aqueous sol type mordants disclosed in 145529 and 54-126027, etc .; Water insoluble mordants disclosed in U.S. Pat. No. 3,898,088; U.S. Pat. No. 4,168,976 (JP-A-54-137333) ) Reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification; and US Pat.
709,690, 3,788,855, 3,642,482, and
3,488,706, 3,557,066, 3,271,147, 3,271,148, JP-A-50-71332, 53-30328, 5
The mordants disclosed in the specifications of 2-155528, 53-125 and 53-1024 can be mentioned.

Among these mordants, those which are difficult to move from the mordant layer to another layer are preferable.

Any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing from about 2 mol% to about 25 mol% silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having an irregular crystal shape such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.1 micron or less or large size grains having a projected area diameter of up to about 10 microns, and it may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. Good.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure (RD), No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation". and types) ”and the same,
No. 18716 (November, 1979), p.648 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chim.
ie et Physique Photographique Paul Montel, 1967),
Duffin, "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chemistry (Foca
Coating Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VLZelikman e
t al, Making and Photographic Emulsion, Focal Press,
1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

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

The silver halide emulsion consisting of the above-mentioned regular grains can be obtained by controlling pAg and pH during grain formation. For more information, see, for example, Photographic Science and Engineering.
eering) Vol. 6, pp. 159-165 (1962); Journal of Photo Science (Journal of Photo)
graphic Science, 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Monodisperse emulsions are silver halide grains having an average grain diameter of greater than about 0.1 micron, at least about 95
Emulsions are typically such that the weight percentage is within ± 40% of the average grain diameter. An average particle diameter of about 0.25 to 2 microns, at least about 95% by weight or at least about 95% in quantity
An emulsion in which the above silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention. Methods for making such emulsions are described in U.S. Pat. Nos. 3,574,628, 3,655,394 and British Patent 1,413,748. Also, JP-A-48-8600, 51-39027, 51-83097, 53-13
7133, 54-48521, 54-99419, 58-37635,
Monodisperse emulsions such as those described in JP-A-58-49938 can also be preferably used in the present invention.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Gutoff, Photographic Science and Engineering,
Volume 14, Pages 248-257 (1970); U.S. Pat. No. 4,434,226
No. 4,414,310, No. 4,433,048, No. 4,439,520, and British Patent No. 2,112,157, and the like. When tabular grains are used,
The advantages of the sensitizing dye such as improvement of color sensitization efficiency, improvement of graininess and increase of sharpness are described in detail in US Pat. No. 4,434,226 cited above.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146,
U.S. Pat.Nos. 3,505,068, 4,444,877 and Japanese Patent Application No. 58
-248469 etc. are disclosed. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Patent Nos. 4,094,684, 4,142,900 and
4,459,353, British Patent 2,038,792, U.S. Patent 4,34
9,622, 4,395,478, 4,433,501, 4,463,087
No. 3,656,962, No. 3,852,067, JP-A-59-162540
No., etc.

Also, a mixture of particles having various crystal forms may be used.

The emulsion of the present invention is usually used after physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the locations thereof are shown in the table below.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. As the dye-forming coupler, a coupler which gives the three primary colors of the subtractive color method (that is, yellow, magenta, and cyan) by color development is important,
Specific examples of the equivalent or 2-equivalent coupler are RD17643, VII described above.
-In addition to the couplers described in the patents of C and D,
The following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat.Nos. 3,408,194 and 3,4
No. 47,928, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-58-10739, U.S. Pat.Nos. 4,401,752 and 4,3.
26,024, RD18053 (April 1979), British Patent No. 1,425,0
No. 20, West German Application Publication No. 2,219,917, No. 2,261,361,
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A-2,329,587 and JP-A-2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat.
1,082, 2,343,703, 2,600,788, 2,9
No. 08,573, No. 3,062,653, No. 3,152,896 and No. 3,936,015. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,
Nitrogen atom leaving groups described in 619 or U.S. Pat.
The arylthio groups described in 51,897 are particularly preferred.
Further, it has a ballast group described in European Patent No. 73,636. 5
-Pyrazolone couplers provide high color density. As the pyrazoloazole coupler, U.S. Pat.
432 pyrazolobenzimidazoles, preferably the pyrazolo [5,1−, described in US Pat. No. 3,725,067.
c] [1,2,4] triazoles, Research Disclosure 24220 (June 1984) and the pyrazolotetrazoles and Research Disclosure 24230 (June 1984) described in JP-A-60-33552 and special features. Kaisho 60-43
The pyrazolopyrazoles described in No. 659 can be mentioned. The imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 are preferable and the pyrazolo [5,1] described in U.S. Pat. No. 4,540,654 in view of low yellow sub-absorption of a coloring dye and light fastness. -B] [1,2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and the naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4 , 1
Representative examples thereof include oxygen atom elimination type two-equivalent naphthol couplers described in Nos. 46,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,171.
No. 2,772,162, No. 2,895,826 and the like.

Couplers capable of forming a cyan dye that is fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include an ethyl group or more at the meta 1-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Phenolic cyan coupler having alkyl group, US Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396, No. 4,334,011
No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365, and the like, 2,5-diacylamino-substituted phenol couplers, U.S. Pat. No. 3,446,62.
No. 2, No. 4,333,999, No. 4,451,559 and No. 4,4
Nos. 27,767 and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position. The cyan couplers described in European Patent No. 161,626A in which the 5-position of naphthol is substituted with a sulfonamide group, an amide group, etc. are also excellent in the fastness of a color image and can be preferably used in the present invention.

In order to correct the unnecessary absorption of the chromophore, it is preferable to mask the color sensitive material for photographing with a colored coupler. U.S. Pat.No. 4,163,670 and JP-B-57-
Typical examples are yellow colored magenta couplers described in 39413 and the like, or magenta colored cyan couplers described in U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Patent 1,146,368. Other colored couplers are described in RD17643, paragraphs VII-G above.

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

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

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the above-mentioned RD17643, VII to F are useful.

A preferred combination with the present invention is JP-A-57-151.
Developer inactivation type represented by 944; U.S. Pat. No. 4,248,962
And the timing type represented by JP-A-57-154234; the reaction type represented by JP-A-59-39653, and particularly preferable are JP-A-57-151944 and JP-A-58-217932. ,
Japanese Patent Application Nos. 59-75474, 59-82214, 59-82214 and
And the reactive DIR couplers described in Japanese Patent Application No. Sho 59-39653 and the like.

In the light-sensitive material of the present invention, a coupler capable of releasing a nucleating agent or a development accelerator or a precursor thereof imagewise during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. A coupler which releases a nucleating agent so as to have an adsorbing action on silver halide is particularly preferable, and specific examples thereof are described in JP-A-59-157638 and JP-A-59-170840.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same, No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD, No. 1
The development process can be carried out by the usual method described in 7643, pp. 28-29 and No. 18716, 651, left column to right column.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β
-Hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Salts of these diamines are generally more stable than those in the free state, and are preferably used.

Color developers include pH buffers such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds or antifoggants. It is common to include agents and the like. If necessary, preservatives such as hydroxylamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dyes. Forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids,
Various chelating agents typified by aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, and antioxidants described in West German Patent Application (OLS) No. 2,622,950 may be added to the color developer.

In the development processing of a reversal color light-sensitive material, black and white development is usually performed before color development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black-and-white developers such as aminophenols such as methyl-p-aminophenol can be used alone or in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Examples of bleaching agents include iron (III), cobalt (III), chromium (VI),
Compounds of polyvalent metals such as copper (II), peracids, quinones,
A nitrone compound or the like is used. Typical bleaching agents are ferrocyanides; dichromates; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid. Aminopolycarboxylic acids or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates; manganates; nitrosophare and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt, diethylenetriaminepentaacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in a stand-alone bleaching solution as well as in a one-bath bleach-fixing solution.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
No. 53, No. 53-65732, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-14162
No. 3, No. 53-28426, Research Disclosure No.
Compounds having a mercapto group or a disulfide group described in 17129 (July 1978) and the like; thiazolidine derivatives as described in JP-A-50-140129; JP-B-45-8
No. 506, JP-A-52-20832, JP-A-53-32735, U.S. Patent No.
Thiourea derivatives described in 3,706,561; West German Patent 1,12
No. 7,715, iodides described in JP-A-58-16235; polyethylene oxides described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; other JP-A-49- 42434, 49-59644, 53-949
No. 27, No. 54-35727, No. 55-26506 and No. 58-163940
The compounds described in No. 1 and iodine and bromine ions can also be used.
Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-956
The compounds described in No. 30 are preferred. Further, U.S. Pat.
The compounds described in No. 834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds thioureas, and a large amount of iodides, but thiosulfate is generally used. As the bleach-fixing solution and the preservative for the fixing solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

After bleach-fixing treatment or fixing treatment, washing treatment and stabilizing treatment are usually carried out. Various known compounds may be added to the washing process and the stabilizing process for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, organic phosphoric acid, bactericides and antibacterial agents that prevent the generation of various bacteria, algae and molds. An agent, a metal salt typified by a magnesium salt or an aluminum salt bismuth salt, a surfactant for preventing drying load or unevenness, and various hardeners can be added as necessary. Or by West Photographic Science and Engineering magazine (LEWest, Phot.S
ci.Eng.), Vol. 6, pp. 344-359 (1965), etc., may be added. It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. Furthermore, instead of the water washing step, JP-A-57-8
You may implement the multistage countercurrent stabilization process process as described in No. 543. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. In addition to the above-mentioned additives, various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia) for adjusting the membrane pH (eg pH 3-9). Representative examples thereof include water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid and the like) and aldehydes such as formalin. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners and other various additives may be used, and two or more of the same or different target compounds may be used. You may use together above.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

Further, in the case of the color photosensitive material for photographing, the (washing-stabilizing) step after fixing which is usually performed can be replaced with the above-mentioned stabilizing step and the washing step (water saving processing). At this time, if the magenta coupler is 2 equivalents, the formalin in the stabilizing bath may be removed.

The washing and stabilizing treatment time of the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, although it varies depending on the type of the photosensitive material and the processing conditions.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, U.S. Pat.
Indoaniline compounds described in No. 7, No. 3,342,599,
Research Disclosure 14850 and Schiff base type compounds described in 15159, aldol compounds described in 13924, metal salt complexes described in US Pat. No. 3,719,492,
Starting with the urethane compounds described in JP-A-53-135628, JP-A-56-6235, JP-A-56-16133, and JP-A-56-59232
No. 56, No. 56-67842, No. 56-83734, No. 56-83735, No. 56
-83736, 56-89735, 56-81837, 56-54430
No. 56-106241, No. 56-107236, No. 57-97531 and No. 57-83565, and various salt-type precursors.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A Nos. 56-64339, 57-144547, and 57-211147.
No. 58, No. 58-50532, No. 58-50536, No. 58-50533, No. 58
-50534, 58-50535 and 58-15438.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the treatment and shorten the treatment time, and conversely to lower the temperature to improve the image quality and improve the stability of the treatment liquid. it can. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

Further, in the case of continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

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

Example 1 In order to evaluate the effectiveness of the compound of the present invention, an emulsion bath as shown below was coated on baryta paper provided with an undercoat layer to prepare Sample 101.

(Sample 101) (Emulsion) Negative silver chlorobromide emulsion (50 mol% silver chloride, average grain size)
0.5μ) 0.42g / m ² Sensitizing dye VI: 5 × 10 ^-4 mol per 1 mol of silver Yellow coupler (C-13) 0.45g / m ² High boiling point organic solvent Oil-2 0.44g / m ² Gelatin 2.2 g / m ² (protective layer) Gelatin 1.3 g / m ² 2,4-dichloro-6-hydroxy-s-triazine sodium salt 50 mg / m ² (Samples 102 to 107) Instead of the yellow coupler C-13 of Sample 101. Comparative compounds C-14, C-15, compounds Y-2, Y-5, Y of the present invention
Sample 101 except substituting equimolar for -10 and Y-12
Samples similar to the above were prepared and used as Samples 102 to 107.

These samples were subjected to sensitomer exposure and processed with a color developer as shown below, and the yellow density of the obtained samples was measured. The results of photographic properties are shown in Table 1.

Color development processing time Temperature 1 Color development 3'30 "33 ° C 2 Bleach-fixing 1'30" 33 ° C 3 Washing with water 2'30 "25-30 ° C The composition of each processing solution in the color development processing is as follows. is there.

Color developing solution Benzyl alcohol 15 ml Diethylene glycol 8 ml Ethylenediaminetetraacetic acid 5 g Sodium sulfite 2 g Anhydrous potassium carbonate 30 g Hydroxylamine sulfate 3 g Potassium bromide 0.6 g 4-Amino-N-ethyl-N- (β-methanesulphonamidoethyl) -m -Toluidine 5g 3/2 Sulfate / monohydrate Add water 1 pH 10.20 Adjust bleach-fixing solution Ethylenediaminetetraacetic acid 2g Ethylenediaminetetraacetic acid Ferric salt 40g Sodium sulfite 5g Ammonium thiosulfate 70g Add water 1 It is clear from the results of the photographic properties in Table 1 that Samples 104 to 107 of the present invention have extremely high color development and high sensitivity with respect to Comparative Sample 101, which reduces the amount of coupler used or the use of silver halide. The amount can be reduced.

Further, from Table 1, couplers Y-2, Y-5, Y-10 and Y-12 having a sulfone or trihalomethyl group at the ortho position of the phenol moiety of the releasing dye which is a compound of the present invention are similar compounds C-14, It is clear that the color density and sensitivity are superior to C-15.

Example 2 Sample 201 was prepared by coating a photosensitive layer shown below on a transparent cellulose triacetate film support provided with an undercoat layer to evaluate the effectiveness of the compound of the present invention.

(Sample 201) (Emulsion) Negative type silver iodobromide emulsion (silver iodide 5 mol%, average thickness 0.15)
μ, tabular grains with an aspect ratio of 7.5: 1) 0.40 g / m ² yellow coupler C-12 0.65 g / m ² high boiling point organic solvent Oil-2 0.7 g / m ² gelatin 3.5 g / m ² (protective layer) gelatin 1.5 g / m ² polymethylmethacrylate particles (diameter 1.5 μm) 0.15 g / m ² 2,4-dichloro-6-hydroxy-s-triazine sodium salt 50 mg / m ² (preparation of samples 202 to 205) sample 201 yellow Samples 202 to 20 were prepared in the same manner as the sample 201 except that the coupler C-12 was replaced with the compounds Y-2, Y-3, Y-11, and Y-13 of the present invention in equimolar amounts.
It was set to 5.

These samples were exposed for sensitometry and subjected to color development processing as shown below. The results of the obtained photographic properties are shown in Table 2.

Treatment process Process time Temperature First development 6'38 ℃ Water wash 2'〃 Inversion 2'〃 Color development 6'〃 Adjustment 2'〃 Bleach 6 ' ′ The composition of the normal temperature dry solution is as follows.

First developer nitrilo-N, N, trimethylenephosphonic acid pentasodium salt
3g Sodium sulfite 20g Hydroquinone monosulphonate 30g Sodium carbonate (monohydrate) 30g 1-Phenyl-4-methyl-4-hydroxymethyl-3pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% Solution) 2 ml Water is added 1000 ml Inversion solution Water 700 ml Nitrilo, N, N, N-trimethylenephosphonic acid, 5 sodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Ice Acetic acid 15 ml Water was added 1000 ml Color developer water 700 ml Nitrilo, N, N, N-trimethylenephosphonic acid-5 sodium salt 3 g Sodium sulfite 7 g Sodium triphosphate (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazine acid 1.5 g N.ethyl-N- (β-methanesulphonamidoethyl) -3 Methyl-4-aminoaniline / sulfate 11g Ethylenediamine 3g Water added 1000ml Adjusted water 700ml Sodium sulfite 12g Sodium sulfite 12g Sodium tetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Water added 1000ml Bleached water 800g Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ethylenediaminetetraacetate iron (III) ammonium (dihydrate) 120.0g Potassium bromide 100.0g Add water 1000ml Fixer water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Heavy Sodium sulfite 5.0g Water added 1000ml Stabilized water 800ml Holimarin (37% by weight) 5.0ml Fuji Drywell 5.0ml Water added 1000ml It is clear from the results of the photographic properties in Table 2 that Samples 202 to 205 of the present invention have extremely high color development and high sensitivity with respect to Comparative Sample 201.

This makes it possible to reduce the amount of coupler used or the amount of silver halide used.

Example 3 (Sample 301) A sample in which a photosensitive layer having the composition shown below was coated on a cellulose triacetate film support provided with an undercoat layer in a multilayer constitution in order to evaluate the effectiveness of the compound of the present invention. Was prepared as Sample 301.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (anti-halation layer) Black colloidal silver …… 0.2 Gelatin …… 1.3 UV absorber UV-1 …… 0.1 Same as above UV-2 …… 0.2 Dispersed oil Oil-1 …… 0.01 Same as above Oil-2 …… 0.01 First 2 layers (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) …… 0.15 Gelatin …… 1.0 Colored coupler C-1 …… 0.1 Same as above C-2 …… 0.01 Dispersion oil Oil-1 …… 0.1 Third layer (First red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 3 mol%, average grain size 0.4 μ) …… Silver 1.7 Gelatin …… 1.6 Sensitizing dye I …… 1.0 × 10 ^-4 Sensitizing dye II …… 2.5 × 10 ^-5 Sensitizing dye III …… 3.5 × 10 ^-5 Sensitizing dye IV …… 2.2 × 10 ^-4 Coupler C-3 …… 0.78 Coupler C-4 …… 0.02 Coupler C-2 …… 0.003 Dispersed oil Oil-1 ...... 0.03 Same as above Oil-3 ...... 0.012 4th layer (2nd red emulsion layer) Silver iodobromide emulsion (7 mol% silver iodide, average grain size 0.8μ) ...... Silver 1.1 gelatin … Sensitized 1.0 sensitizing dye I ...... 7.0 × 10 ^-5 dye II ...... 2.0 × 10 ^-5 Sensitizing dye III ...... 2.5 × 10 ^-4 Sensitizing dye IV ...... 2.0 × 10 ^-4 Coupler C-5 ... … 0.06 Coupler C-6 …… 0.017 Coupler C-2 …… 0.01 Dispersion oil Oil-1 …… 0.01 Same as above Oil-2 …… 0.05 Fifth layer (intermediate layer) Gelatin …… 1.0 Compound Cpd-A …… 0.03 Dispersion Oil-1 …… 0.05 Same as above Oil-2 …… 0.05 Sixth layer (first green emulsion layer) Silver iodobromide emulsifier (silver iodide 4 mol%, average grain size 0.4μ) …… 0.85 Sensitizing dye V …… 2.0 × 10 ^-4 Sensitizing dye VI …… 4.5 × 10 ^-4 Gelatin …… 1.0 Coupler C-7 …… 0.33 Coupler C-4 …… 0.06 Coupler C-1 …… 0.15 Dispersion oil Oil-1… ... 0.5 seventh layer (second green-sensitive emulsion layer) silver iodobromide emulsion (silver iodide 6 mol%, average particle size 0.7 .mu.m) ...... silver 0.9 gelatin ...... 1.0 sensitizing dye V ...... 1.0 × 10 ^{- 4} Sensitizing dye VI ...... 1.9 × 10 ^-4 Coupler C-9 …… 0.05 Coupler C-10 …… 0.01 Coupler C-11 …… 0.08 Coupler C-1 …… 0.02 Coupler C-8 …… 0.02 Dispersed oil Oil-1 …… 0.10 Same as above Oil-2 …… 0.05 8th layer ( Yellow filter layer) Gelatin ...... 1.2 Yellow colloidal silver ・ ・ ・ 0.08 Compound Cpd-B ・ ・ ・ 0.1 Dispersion oil Oil-1 ・ ・ ・ 0.3 9th layer (1st blue sensitive emulsion layer) Monodispersed silver iodobromide emulsion (iodination) Silver 4 mol%, average particle size 0.3 μ) ...... Silver 0.4 Gelatin ...... 1.0 Sensitizing dye VIII …… 2 × 10 ^-4 Coupler C-12 …… 0.9 Coupler C-5 …… 0.07 Dispersion oil Oil-1…. 0.2 0.2th layer (second blue emulsion layer) Silver iodobromide (silver iodide 10 mol%, average grain size 1.5 μ) ...... Silver 0.5 gelatin ...... 0.6 Sensitizing dye VIII …… 1 × 10 ^-4 Coupler C-13 0.25 Dispersion oil Oil-1 0.07 11th layer (1st protective layer) Gelatin 0.8 UV absorber UV-1 0.1 Same as above UV-2 0.2 Dispersion oil Oil-1 …… 0.01 Dispersion oil Oil-2 …… 0.01 12th layer (second protective layer) Fine silver bromide (average particle size 0.07μ) …… 0.5 Gelatin …… 0.45 Polymethylmethacrylate particles (diameter 1.5 μ) 0.2 Hardener H-1 0.4 Formaldehyde scavenger S-1 1.0 In addition to the above components, a surfactant was added to each layer as a coating aid.

(Sample 302) Instead of the yellow coupler C-12 in the ninth layer of Sample 301, the comparative compound C-14 was replaced by reducing it to 90 mol%, and the dispersion oil Oil-1 was changed from 0.20 g / m ^{2 accordingly.} 0.18g
/ m ² and reduce the amount of gelatin from 1.0 g / m ² to 0.9 g
A sample 302 was prepared in the same manner as the sample 301 except that it was reduced to / m ² .

(Samples 303 and 304) Instead of the yellow coupler C-12 in the ninth layer of Sample 301, the compounds Y-1 and Y-3 of the present invention were replaced by reducing the amount used to 65 mol%, and the dispersion oil Oil- 1 to 0.2
Reduce from 0 g / m ² to 0.13 g / m ^2, gelatin from 1.0g / m ² 0.
Sample 30 was prepared in the same manner as Sample 301 except that the amount was reduced to 7 g / m ^2.
Created 3, 304.

(Samples 305 and 306) Instead of the yellow coupler C-12 in the ninth layer of Sample 301, the compounds Y-5 and Y-15 of the present invention were replaced by reducing the usage amount to 60 mol%, and accordingly, the dispersed oil Oil- 1 to 0.2
Reduce from 0 g / m ² to 0.13 g / m ^2, gelatin from 1.0g / m ² 0.
Sample 30 was prepared in the same manner as Sample 301 except that the amount was reduced to 7 g / m ^2.
Created 5, 306.

(Samples 307 and 308) In place of the yellow coupler C-12 of the ninth layer of Sample 301, the compounds Y-6 and Y-16 of the present invention were replaced by reducing the used amount to 60 mol%, and accordingly the dispersed oil Oil- 0.20 g / m
Reduced from ² to 0.13g / m ² and gelatin from 1.0g / m ² to 0.7g / m
Samples 307 and 308 are the same as sample 301 except that the number is reduced to ^2.
It was created.

The samples 301 to 308 prepared as described above were subjected to sensitometric exposure with white light and developed with a color developer as shown below.

These treated samples gave almost similar sensitometry. A comparison of the sharpness of the yellow color images of these samples
Table 3 shows MTF values at 40 frequencies per m.

The method of measuring MTF is described in "The Theory of the Photogratic Process", edited by THJames.
phic Process) Fourth Edition "(Mac-Millan, 1977), pages 604-607.

The chemical structural formulas or chemical names of the compounds used in the above examples are shown below.

Oil-1 Tricresyl phosphate Oil-2 Dibutyl phthalate Oil-3 Bis (2-ethylhexyl) phthalate Color development process (38 ℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds Treatment used for each step The liquid composition was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Water added 1.0l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water added 1.0 l pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added 1.0 l pH 6.6 Stabilizer formalin (40%) 2.0 ml Polyoxy Ethylene-P-monononylphenyl ether (average degree of polymerization about 10) 0.3g Add water to 1.0l As is clear from Table 3, samples using the compound of the present invention
303 to 308 have a higher MTF value than Comparative Samples 301 and 302, and it is clear that the present invention provides color photographic light-sensitive materials having improved sharpness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-54-145135 (JP, A)

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material containing a compound represented by the following general formula (IA). General formula (IA) However, A is the general formula (IB) Represents In the above formula, L ₁ represents —SO ₂ L ₁₀ or —C (L ₁₁ ) ₃ . L ₁₀ represents an aliphatic group, an aromatic group, a heterocyclic group, or an amino group, each of which may be unsubstituted or may have a substituent, L 10
₁₁ represents a halogen atom. At least one of L ₂ and L ₃ represents an electron-withdrawing group. L ₄ , L ₅ , L ₆ , L ₇ , L ₈ , L ₉ ,
And L ₂ and L ₃ other than the case of representing an electron-withdrawing group are each independently a hydrogen atom, a halogen atom, an aliphatic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxy group, an aryloxy group, Represents a carbonamido group, a sulfonamide group, a ureido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, a cyano group, and a nitro group, and groups other than a hydrogen atom, a halogen atom, a cyano group, and a nitro group are substituents. May have. L ₃ and L ₄ , L ₈ and L ₉ , and L ₅ and L ₆ may be bonded to each other to form a 5-membered to 7-membered ring. Time represents a timing group, and n represents an integer of 0 or more. Cp represents a coupler residue that binds to Time _n at the coupling position. Time _n is a trivalent group, and Cp
May have a non-coupling position and / or a bond with PUG (bond represented by a dotted line in the general formula (IA)). X is -O-, -S-, or And L ₁₂ represents a hydrogen atom, an aliphatic group, an aromatic group, or an acyl group.