JPH05100379A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic image superior in color reproduction performance and sharpness by incorporating >=2 kinds of specified magenta couplers in a green-sensitive layer and a specified compound in the constituent layers of the photosensitive material. CONSTITUTION:The green-sensitive layer contains >=2 kinds of the magenta dye-forming couplers having maximum absorption wavelengths different from each other by 5nm and represented by formula I in which each of R1 and R2 is H or a substituent: X is H or a group to be released at the time of reaction with the oxidation product of a developing agent. At least one of the constituent layers of the photosensitive material contains at least one of the compounds represented by formulae II and III in which R11 is R14-N(R16)CON(R15)-; R14 is alkyl or the like; each of R15 and R16 is H or the like; each of R12 and R13 H or the like; B is a group releasing X after being released from the oxidation product of the hydroquinone ring; X is a development inhibitor; Q<1> is an atomic group necessary to form a hetero ring containing a hetero atom; and R<21> is a group substitutable on the hydroquinone ring.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a light-sensitive material excellent in color reproducibility and sharpness.

[0002]

The formation of a dye image in a silver halide color photographic light-sensitive material usually involves reducing the silver halide grains in the silver halide color photographic light-sensitive material exposed to an aromatic primary amine color developing agent. It is oxidized at this time, and this oxidant is subjected to a coupling reaction with a coupler previously contained in the silver halide color photographic light-sensitive material. In a silver halide color photographic light-sensitive material, three types of couplers that form dyes of yellow, magenta and cyan are usually used in order to perform color reproduction by a subtractive method.

Of these, the 5-pyrazolone-based magenta couplers, which are commonly used as magenta couplers, have major problems in color reproduction such that the magenta coloring dye has a sub-absorption at around 430 nm and the long-wavelength tail is poor. Met.

Recently, US Pat. No. 3,061,432,
No. 3,725,067, No. 4,500,630, Research Disclosure No. 24220 (198
June 4), the same No. 24230 (June 1984),
JP-A-58-42045, JP-A-59-171956,
By using a pyrazoloazole-based magenta coupler as disclosed in JP-A-60-43659 and JP-A-60-190779, it is possible to suppress the sub-absorption of the magenta color-forming dye, thereby improving the magenta saturation. Was given.

However, in the above-mentioned pyrazoloazole-based magenta coupler, since the absorption of the yellow component and the cyan component is small, the region not absorbed by the cyan, magenta and yellow dyes is expanded, and the spectral absorption waveform of the magenta coloring dye shows the coloring density. There was a drawback that it changed due to. In order to improve the drawback, Japanese Patent Laid-Open No. 3-1
No. 60441 discloses a method of using two kinds of magenta couplers having different maximum absorption wavelengths of color development, but the effect was insufficient.

[0006] In recent years, means for achieving high image quality in a small format have been developed one after another, but it is not sufficient yet, and further technical improvement is required. It is currently common practice to use DIR compounds to improve sharpness and interimage effects. What is usually used is a DIR coupler which releases a development inhibitor imagewise to form a coloring dye by a coupling reaction with an oxidation product of a color developing agent, but the dye produced by the coupling reaction is a main coupler. When it is different from the dye obtained from (1), color turbidity occurs, which is not preferable for color reproduction. From these things, a colorless DIR compound has been demanded.

Colorless DIR compounds are classified into two types, a coupling type and a redox type, depending on the reaction mode with an oxidant of a color developing agent. Of these, the coupling type is disclosed, for example, in Japanese Patent Publication Nos. 51-16141 and 51-16142, and U.S. Pat. No. 4,226,943.
Nos. 4,371,223 and the like, and the redox type compounds are described in, for example, U.S. Pat. No. 3,379,52.
9, No. 3,639,417, JP-A-49-129.
536, 64-546 and the like, DIR hydroquinone compounds, or JP-A-61-213847,
64-88451, U.S. Pat. No. 4,684,604.
There are DIR hydrazide compounds described in No. These DIR compounds can improve image sharpness and color reproducibility by the edge effect and the inter-image effect, but they are still insufficient and further improvement has been strongly desired.

[0008]

The first object of the present invention is to provide a silver halide color photographic light-sensitive material having high color saturation and excellent color reproducibility.

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

[0010]

The objects of the present invention have been solved by the following means.

That is, in a silver halide color photographic light-sensitive material having at least one blue-sensitive layer, green-sensitive layer and red-sensitive layer on a support, the green-sensitive layer is represented by the general formula (M Among the magenta dye-forming couplers represented by the formula (4), at least two couplers differing in the maximum color development absorption wavelength by 5 nm or more, and at least one layer constituting the light-sensitive material has the general formula (I) or the following chemical formula (6). A silver halide color photographic light-sensitive material comprising at least one compound represented by the general formula (II)

[0012]

[Chemical 4]

[0013]

[Chemical 5]

[0014]

[Chemical 6] In the general formula (M), R ₁ and R ₂ each represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group which leaves upon reaction with an oxidized product of a developing agent.

In the general formula (I), R ₁₁ is R ₁₄ --N
_{(R 16) CON (R 15} ) -, R 14 OCON (R 15) -,
_{R 14 SO 2 N (R 15} ) -, R 14 -N (R 16) SO 2 N
(R ₁₅₎ - or represents a R ₁₇ CONH-. Where R ₁₄
Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group or an aryl group, and R ₁₇ represents a hetero atom at a carbon atom adjacent to the carbonyl group. It represents an unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group having 2 or more carbon atoms. R
₁₂ and R ₁₃ are hydrogen atoms or Hammett's substituent constant σ
_p represents a substituent of 0.3 or less, B represents a group which releases X after leaving the hydroquinone mother nucleic acid product, X represents a development inhibitor, k represents an integer, and A and A ′ represent hydrogen atoms. Alternatively, it represents a group that can be removed with an alkali.

In the general formula (II), Q ¹ contains at least one hetero atom, and is 5 together with the carbon atom to be bonded.
Represents a group of atoms necessary to form a heterocyclic ring having at least one member ring,
R ²¹ represents a group capable of substituting for the hydroquinone nucleus,
B, X, k, A and A ′ have the same meanings as described in the general formula (I).

First, the general formula (M) in the present invention will be described in detail.

In the general formula (M), R ₁ and R ₂ each represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

R ₁ , R ₂ and X will be described in detail.

R ₁ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group. , Anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxy It represents a carbonyl group, an acyl group or an azolyl group, and R ₁ may be a divalent group to form a bis form.

More specifically, R ₁ is each a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom), an alkyl group (eg a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). , An alkynyl group, a cycloalkyl group, and a cycloalkenyl group, and specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-Pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl) , 4-tetradecanamidophenyl), a heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, an alkoxy group (for example, methoxy). ,
Ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy groups (eg phenoxy, 2-methylphenoxy, 4-t
-Butylphenoxy, 3-nitrophenoxy, 3-t-
Butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), an acylamino group (eg acetamide,
Benzamide, tetradecane amide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t
-Butyl-4-hydroxyphenoxy) butanamide,
2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino group (for example, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), anilino group (for example, phenylamino, 2-chloroanilino, 2 -Chloro-5
Tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino,
2-chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), a ureido group (for example, phenylureido, methylureido, N,
N-dibutylureido), a sulfamoylamino group (for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), an alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2- Phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2- Carboxyphenylthio, 4-
Tetradecanamide phenylthio), an alkoxycarbonylamino group (eg methoxycarbonylamino, tetradecyloxycarbonylamino), a sulfonamide group (eg methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-).
Dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (Eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyltetrazole) 5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, Acetoxy), a carbamoyloxy group (eg N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg phenoxycarbonylamino), an imide group (eg N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), heterocyclic thio group (for example, 2-
Benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (for example, dodecanesulfinyl,
3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (eg phenoxycarbonyl), acyl group (eg acetyl,
3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (eg imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl,
Triazole). Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁ is alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group, urethane group,
An acylamino group can be mentioned.

R ₂ is a group having the same meaning as the substituent exemplified for R ₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group,
It is an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, or an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group or an arylthio group.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. The releasable group is specifically described as a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl or aryl sulfonyloxy group, an acylamino group, an alkyl or aryl sulfonamide group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl group. , An aryl or heterocyclic thio group, a carbamoylamino group, a 5-membered or 6-membered nitrogen-containing heterocyclic group, an imide group, an arylazo group, etc., and these groups are further substituted with a group acceptable as a substituent of R _1. It may have been done.

More specifically, the releasable group is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom),
Alkoxy group (eg ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryloxy group (eg 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxy) Phenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-
Carboxyphenoxy), acyloxy groups (eg acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl sulfonyloxy groups (eg methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg dichloroacetylamino, heptafluorobutyrylamino) ), An alkyl or aryl sulfonamide group (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (eg, phenoxy). Carbonyloxy), alkyl,
Aryl or heterocyclic thio groups (eg dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (eg N-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocycle (eg imidazolyl, pyrazolyl, triazolyl, tetrazolyl) ,
1,2-dihydro-2-oxo-1-pyridyl), an imide group (for example, succinimide, hydantoinyl), an arylazo group (for example, phenylazo, 4-methoxyphenylazo), and the like. In addition to these, X is an aldehyde or ketone as a leaving group bonded via a carbon atom.
It may also take the form of a bis-type coupler obtained by condensing an equivalent coupler. Further, X may contain a photographically useful group such as a development inhibitor or an accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom.

Specific examples of the compound represented by the general formula (M) are shown in the following chemical formulas 7 to 34, but the invention is not limited thereto.

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

[0040]

[Chemical 20]

[0041]

[Chemical 21]

[0042]

[Chemical formula 22]

[0043]

[Chemical formula 23]

[0044]

[Chemical formula 24]

[0045]

[Chemical 25]

[0046]

[Chemical formula 26]

[0047]

[Chemical 27]

[0048]

[Chemical 28]

[0049]

[Chemical 29]

[0050]

[Chemical 30]

[0051]

[Chemical 31]

[0052]

[Chemical 32]

[0053]

[Chemical 33]

[0054]

[Chemical 34] Next, a general method for synthesizing the coupler represented by the general formula (M) will be described. 1 represented by the general formula (M)
The synthesis of the H-pyrazolo (5,1-c) -1,2,4-triazole skeleton is described in US Pat. No. 3,725,067, JP-B-47-27411, JP-A-48-30895, and JP-A-54-3095. -145135, Research Disclosure 12443, J. Am. Chem. Soc. Perkin
I. It can be synthesized by the method described on page 2047 (1977).

Further, it can be synthesized according to the method described in JP-A-2-134354.

A general method for introducing a coupling-off group will be described below. (1) Method of introducing a halogen atom according to the reaction of the following chemical formula 35

[0057]

[Chemical 35] The halogenation at the coupling active position is carried out by adding 1 equivalent of bromine, N-bromosuccinimide, sulfuryl chloride, or N-chlorosuccinimide to a 4 equivalent coupler (A) in an inert solvent such as dichloromethane. It can be easily obtained by acting. (2) Method of linking oxygen atoms (a) Substituting a phenoxy group for a halogen atom of a coupler having a halogen atom at the coupling active position according to the reaction of the following Chemical Formula 36.

[0058]

[Chemical 36] The halogenated compound (B) was converted to dimethylformamide (DM
F), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), N-methyl-
In an aprotic polar solvent such as 2-pyrrolidone,
Suitable _{R 5 -OM, (R 5 -O} ) 2 M ' or (R ₅ -
O) ₃ M ″ (R ₅ represents an aryl group, M, M ′ and M ″ represent monovalent, divalent and trivalent metal ions, respectively) to obtain the desired coupling activity. (C) in which an aryloxy group is introduced at the position is obtained. Preferably, the halogenated compound (B) is used in an equivalent amount of 50
It is desirable to react with an equivalent to 20 times amount (molar ratio) of a suitable sodium salt or potassium salt of phenol at a temperature of 50 ° C. to 150 ° C. in a double amount (weight) of the above solvent. Further, in this reaction, the reaction may be accelerated by adding a quaternary ammonium salt such as tetrabutylammonium bromide or an alkali metal halide such as cesium bromide.

(B) A method of forming an 1H-pyrazolo [5,1-c] -1,2,4-triazole skeleton after introducing an aryloxy group into the active methylene of β-ketonitrile according to the reaction shown below.

[0060]

[Chemical 37] The halogenated compound (E) obtained by treating 3-oxonitrile (D) with a halogenating agent such as bromine or sulfuryl chloride in an inert solvent such as dichloromethane is converted to a suitable R _{5 in} the presence of a tertiary amine. The aryloxy derivative (F) is obtained by treating with —OH or treating with a metal salt such as R ₅ —OM described in (2) above. Aminopyrazole obtained by reacting this with foam water hydrazine in a solvent such as ethanol, a diazonium salt is synthesized using sodium nitrite or isoamyl nitrite and an acid (for example, hydrochloric acid or sulfuric acid), and this diazonium salt is Treatment with a reducing agent such as stannous chloride, sodium sulfite and sodium hydrosulfite gives a hydrazinopyrazole body (H). The target coupler can be synthesized from this (H) form according to the above-mentioned skeleton synthesis method.

3-oxonitrile (D) is described in US Pat. No. 4,411,753, German Patent Publication DE 3,209,
472 and Synthesis, 472 (1
977) and the like. (3) Method of linking sulfur atom A coupler having an aromatic mercapto or heterocyclic mercapto group substituted at the 7-position is a method described in US Pat. No. 3,227,554, that is, an aryl mercaptan, a heterocyclic mercaptan and its corresponding The disulfide can be synthesized by dissolving it in a halogenated hydrocarbon solvent and adding chlorine or sulfuryl chloride as a sulfenyl chloride to a 4-equivalent coupler dissolved in an aprotic solvent. As a method for introducing an alkylmercapto group at the 7-position, a method described in U.S. Pat. No. 4,264,723, that is, a method of introducing a mercapto group at the coupling active position of a coupler and allowing a halide to act on the mercapto group, and S A method of synthesizing in one step by using-(alkylthio) isothiourea and hydrochloride (or bromine-hydrochloric acid) is effective. (4) Method of connecting nitrogen atoms (a) Method of introducing amino group into coupling active position and modifying the amino group.

The introduction of an amino group at the coupling active position can be carried out by the method shown in US Pat. No. 3,419,391,
That is, it can be easily obtained by nitrosating the coupling active position, reducing it with an appropriate method, and modifying the resulting amino compound. Further, by coupling a diazonium salt derived from, for example, aniline anthranilic acid, and sulfanilic acid to the coupling active site to obtain an azo dye, which is then reduced with a suitable reducing agent such as hydrosanphyto soda. It can be easily obtained by modifying the resulting amino compound.

(B) A method in which a halogen atom is introduced at the coupling active site and the halogen atom is replaced with an R ₈ (R ₉ ) N-group.

R ₈ or R ₉ is an alkyl group, an aryl group, a heterocyclic group, and R ₈ and R ₉ are bonded to each other,
A nitrogen heterocyclic group capable of forming a 5-membered ring or a 6-membered ring with a nitrogen atom, wherein R ₈ (R ₉ ) N- and the halogen-substituted compound (B) are alcohol-based at a temperature range of 0 ° C to 180 ° C. It can be obtained by dissolving in a solvent aprotic polar solvent, halogenated hydrocarbon solvent or the like and reacting in the presence of a suitable base.

The object of the present invention can be achieved by using at least two kinds of magenta couplers represented by the general formula (M), which have a maximum absorption wavelength for color development different by 5 nm or more.

That is, of the two kinds of magenta couplers, the one having the shorter maximum color development absorption wavelength is coupler S and the one having the longer maximum color development absorption wavelength is coupler L, and the maximum color development absorptions λ max S and λ max L of coupler S and coupler L are 500-600
, and the difference between λmax S and λmax L must be at least 5 nm.

Here, the maximum color development absorption is the maximum absorption wavelength of the spectral absorption spectrum of the color image obtained through color development processing of the color reversal light-sensitive material of the present invention. It is a value obtained from measurement of a spectral absorption spectrum of a color image obtained by development processing.

When the green-sensitive unit is composed of two or more emulsion layers in the present invention, the layer containing coupler S and coupler L is preferably a high-sensitivity layer. In any green-sensitive layer, coupler S and coupler L are included. It is more preferable to use a layer containing

In the emulsion layer containing the coupler S and the coupler L, the ratio of the coupler S to the coupler L can be arbitrarily selected, but the coupler S is preferably 10 to 90 mol%, and 30 to 70 mol%. The range is more preferably.

The addition amount of the coupler represented by formula (M) of the present invention is in the range of 0.001 to 2 mol, preferably 0.01 to 0.5 mol, per 1 mol of silver in the emulsion layer. It is generally used.

Next, the general formula (I) will be described in more detail.

R ¹¹ in the general formula (I) is R ¹⁴ —N (R ¹⁶ ).
CON (R ¹⁵ ) −, R ¹⁴ OCON (R ¹⁵ ) −, R ¹⁴ SO
₂ N (R ¹⁵ )-, R ¹⁴ -N (R ¹⁶ ) SO ₂ N (R ¹⁵ )-
Alternatively, it represents R ¹⁷ CONH-. Here, R ¹⁴ is a substituted or unsubstituted alkyl group (having 1 to 30 carbon atoms, for example, methyl, ethyl, isopropyl, decyl, hexadecyl,
t-butyl, cyclohexyl, benzyl), a substituted or unsubstituted alkenyl group (having 2 to 30 carbon atoms, for example, 1-
Butenyl, 1-octadecenyl), a substituted or unsubstituted alkynyl group (having 2 to 30 carbon atoms, such as ethynyl, 1
-Octynyl), a substituted or unsubstituted aryl group (having 6 to 30 carbon atoms, for example, phenyl, naphthyl, 3-dodecaneamidophenyl, 3-hexadecanesulfonamidophenyl, 4-dodecyloxyphenyl), or a heterocyclic group (N, 5- to 20-membered compounds containing at least one hetero atom of O, S and Se, for example, 4-pyridyl, 2-furyl, pyrrolo, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, triazolyl, tetrazolyl, Benzotriazolyl, morpholinyl). R
Examples of the substituent of ¹⁴ include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxylic acid amide group, a sulfonic acid amide group, an alkoxycarbonylamino group, a ureido group, a carbamoyl group, and an alkoxy group. Carbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom,
Examples thereof include an acyl group, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group and a heterocyclic group.

R ¹⁵ and R ¹⁶ may be the same or different, and examples thereof include a hydrogen atom and those represented by R ¹⁴ . R ¹⁵ is preferably a hydrogen atom.

R ¹⁷ is a substituted or unsubstituted alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom (preferably 2 to 30 carbon atoms,
For example, ethyl, nonyl, pentadecyl, isopropyl,
t-butyl, 1-hexylnonyl, 3- (2,5-di-
t-pentylphenoxy) propyl, cyclohexyl,
Benzyl), a substituted or unsubstituted alkenyl group (having 2 to 30 carbon atoms, such as vinyl, 1-octenyl, 2-phenylvinyl), a substituted or unsubstituted alkynyl group (having 2 to 30 carbon atoms, such as ethynyl, phenylethynyl) ,
A substituted or unsubstituted aryl group (having 6 to 30 carbon atoms, such as phenyl, naphthyl, 3,5-bis (octadecaneamido) phenyl, 2-hexadecanesulfonamidophenyl, 4-dodecyloxyphenyl), or a heterocyclic group (N , 5-, 20-membered ones containing at least one hetero atom of O, S, Se, for example 3-pyridyl,
2-furyl, 3-thiazolyl, benzotriazolyl, benzimidazolyl).

Examples of the substituent of R ¹⁷ include those mentioned as the substituent of R ¹⁴ .

As R ₁₂ and R ₁₃ in the general formula (I), hydrogen atom or Hammett's substituent constant σ _p is 0.3.
The following substituents are represented, and examples thereof include an alkyl group (having 1 to 30 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, decyl, hexadecyl, cyclohexyl, benzyl, t-octyl), an aryl group (having a carbon number of 6
To 30, for example, phenyl, naphthyl, an alkoxy group (having 1 to 30 carbon atoms, for example, methoxy, hexyloxy,
Hexadecyloxy, 2-dodecyloxy, benzyloxy), aryloxy groups (C6-30, such as phenoxy, naphthoxy), alkylthio groups (C1-C1).
30, for example, methylthio, hexylthio, dodecylthio, benzylthio), an arylthio group (having 6 to 3 carbon atoms).
0, for example, phenylthio, naphthylthio, 2-butyloxy-5-t-octylphenyl), amide group (having 1 to 30 carbon atoms, such as acetamide, butanamide, hexadecanamide, benzamide), sulfonamide group (having 1 to 30 carbon atoms, for example, Methanesulfonamide, octanesulfonamide, hexadecanesulfonamide, benzenesulfonamide), ureido group (having 1 to 30 carbon atoms, for example, 3-methylureido, 3-dodecylureido, 3-
Phenylureido), urethane group (having 2 to 30 carbon atoms, such as methoxycarbonylamino, decyloxycarbonylamino, phenoxycarbonylamino), sulfamoylamino group (having 30 or less carbon atoms, such as 3-methylsulfamoylamino, 3- Phenylsulfamoylamino), a halogen atom (for example, chlorine, bromine, fluorine), a hydroxy group or-(B) _k- X.

R ¹² and R ¹³ may have a substituent,
Examples of those substituents include those mentioned as the substituents possessed by R ¹⁴ .

Next, the general formula (II) will be described in detail.

Q ^{1 in the} general formula (II) is a divalent group containing at least one hetero atom, and examples thereof include an amide bond, a divalent amino group, an ether bond, a thioether bond and an imino group. Examples thereof include a bond, a sulfonyl group, a carbonyl group, an alkylene group, an alkenylene group, and the like, which may be a group obtained by combining a plurality of these and may further have a substituent. However, when Q ¹ contains an ether bond, it is not a 5-membered ring.

Examples of the heterocyclic ring completed by Q ¹ are shown in the following chemical formulas 38 and 39.

[0081]

[Chemical 38]

[0082]

[Chemical Formula 39] R ²¹ is a group capable of substituting on the hydroquinone mother nucleus, and specifically, in addition to the group described for R ¹³ in the general formula (I), a substituent,
An unsubstituted acyl group (preferably having 1 to 30 carbon atoms,
For example, acetyl, octanoyl, benzoyl, chloroacetyl, 3-carboxypropionyl, octadecanoyl), substituted or unsubstituted alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonyl, octyloxycarbonyl, phenoxycarbonyl, Octadecyloxycarbonyl, methoxyethoxycarbonyl), a substituted or unsubstituted carbamoyl group (preferably having 1 to 30 carbon atoms, for example, carbamoyl, N-propylcarbamoyl, N-hexadecylcarbamoyl,
N- {3- (2,4-di-tert-pentylphenoxy) propyl}, N-phenylcarbamoyl, N- (3
-Dodecyloxybutyl), pyrrolidinocarbonyl),
Substituted or unsubstituted sulfamoyl group (preferably having 0 carbon atoms)
-30, for example, sulfamoyl, dibutylsulfamoyl), a substituted or unsubstituted sulfonyl group (preferably having 1 to 30 carbon atoms, for example, methanesulfonyl, benzenesulfonyl, p-dodecylbenzenesulfonyl) or a heterocyclic group ( 5- to 20-membered compounds containing at least one of N, O, S, and Se, such as 5-tetrazolyl, 2-benzoxazolyl, 2-thiazolyl, 2-imidazolyl, 2-pyridyl, and morpholino. Be done.

A, A ', B and X in the above general formulas (I) and (II) will be described in detail.

In the general formulas (I) and (II), when A and A'represent a group which can be removed by an alkali (hereinafter referred to as a precursor group), preferably an acyl group,
Hydrolyzable groups such as alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imidoyl group, oxalyl group, and sulfonyl group, US Pat.
No. 009,029, a type of precursor group utilizing the reverse Michael reaction, and a type of precursor utilizing an anion generated after the ring opening reaction described in US Pat. No. 4,310,612 as an intramolecular nucleophilic group. Based on US Pat. No. 3,6
Precursor groups, in which the anion described in 74,478, 3,932,480 or 3,993,661 causes electron transfer through a conjugated system to cause a cleavage reaction, U.S. Pat. No. 4,335,335. Precursor groups described in US Pat. No. 200, which cause a cleavage reaction by electron transfer of anions reacted after ring cleavage, or US Pat. No. 4,363,8.
No. 65, No. 4,410,618, and precursor groups utilizing an imidomethyl group.

The groups represented by B in the general formulas (I) and (II) are-(B) _k after the hydroquinone mother nucleus is oxidized by the oxidized form of the developing agent during development to form a quinone form.
-A coupler which emits X and represents a divalent group capable of releasing X thereafter, and which may have a timing adjusting function, and which releases X in response to another molecule of an oxidized developing agent. Or a redox group. Here, when k is 0, it means that X is directly bonded to the hydroquinone mother nucleus, and when k is 2 or more, the same or different combinations of two or more B's are represented.

When B is a group having a timing adjusting function, for example, US Pat. Nos. 4,248,962 and 4,409,323 and British Patent 2,096,783 are used.
U.S. Pat. No. 4,146,396, JP-A-51-1
46828, JP-A-57-56837, and the like. The Time may be a combination of two or more selected from those described in these.

Preferred examples of the timing control group include:
The following are listed. (1) Group utilizing cleavage reaction of hemiacetal: For example, US Pat. No. 4,146,396, JP-A-60-2.
49148 and 60-249149. (2) Group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction: For example, a timing group described in US Pat. No. 4,248,962 can be mentioned. (3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system: for example, US Pat. No. 4,409,323.
Or No. 4,421,845. (4) Group utilizing cleavage reaction by hydrolysis of ester: For example, a linking group described in West German Laid-Open Patent No. 2,626,315. (5) Group utilizing cleavage reaction of imino ketal: For example, a linking group described in US Pat. No. 4,546,073.

Examples of the group represented by B which is a coupler or a redox group include the following.

As the coupler, for example, in the case of a phenol-type coupler, the one bonded to the hydroquinone nucleus at the oxygen atom excluding the hydrogen atom of the hydroxyl group. In the case of a 5-pyrazolone type coupler,
It is bonded to a hydroquinone nucleus at an oxygen atom obtained by removing a hydrogen atom from a hydroxy group of a tautomerism of hydroxypyrazole.

Each of these functions as a coupler only after leaving the hydroquinone nucleus, and reacts with an oxidized product of a developing agent to release X bonded to their coupling positions.

Preferred examples of the case where B is a coupler include formulas (C-1) to (C-4) shown below.
Can be given.

[0092]

[Chemical 40] In the formula, V ₁ and V ₂ represent a substituent, and V ₃ , V ₄ ,
V ₅ and V ₆ represent a nitrogen atom or a substituted or unsubstituted methine group, V ₇ represents a substituent, x represents an integer of 0 to 4, and when x is plural, V ₇ is the same or different. And two V _7's may be linked to each other to form a cyclic structure. V ₈ is a —CO— group, —SO ₂ —
Group, an oxygen atom or a substituted imino group, and V ₉ is -V
₈ -N-C = C-together represents a nonmetallic atom group for forming a 5- to 8-membered ring, V ₁₀ represents a hydrogen atom or a substituent. Where * is to the hydroquinone nucleus, and *
* Means to bond to X.

In the general formulas (I) and (II), when the group represented by B is a redox group, it is preferably represented by the formula (R-1) shown below.

[0094]

[Chemical 41] In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, at least one of n X ′ and Y represents a methine group having —X as a substituent, and other X ′ And Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n is 1 to 3
(Wherein n X'and n Y are the same or different), A represents a hydrogen atom or a group removable by an alkali, and has the same meaning as A in the general formula (I). have. Here, the case where any two substituents of P, X ', Y, Q and A become a divalent group and are connected to each other to form a cyclic structure is also included. For example (X '=
Y) _n is a case where _n forms a benzene ring, a pyridine ring, or the like.

Of the groups represented by the formula (R-1), a particularly preferred group is the formula (R-2) or (R
-3).

[0096]

[Chemical 42] In the formula, the * mark represents the position of bonding to the hydroquinone mother nucleus, and the ** mark represents the position of bonding to X.

R ₆₄ in the formula represents a substituent, and q is 0, 1
Represents an integer of 3 to 3. When q is 2 or more, two or more R _64's may be the same or different, and when two R _64's are substituents on adjacent carbons, they are each a divalent group and linked to each other to represent a cyclic structure. It also includes cases.

Examples of R ₆₄ include those mentioned for R ²¹ in the general formula (II).

In formulas (I) and (II), X means a development inhibitor residue. As a preferable example of X, a compound having a mercapto group bonded to the heterocycle represented by the formula (X-1) shown in the following chemical formula 43, or the following chemical formula 4
Examples thereof include a heterocyclic compound represented by the formula (X-2) and capable of producing imino silver.

[0100]

[Chemical 43] In the formula, Z ₁ represents a nonmetallic atom group necessary for forming a monocyclic ring or a condensed ring heterocycle, and Z ₂ represents a nonmetallic atom necessary for forming a monocyclic ring or a condensed ring heterocycle with N. Represents a group. These heterocycles may have a substituent, and * represents a position bonded to B. Z ₁ and Z ₂
The heterocycle formed by is more preferably a 5-membered to 8-membered heterocycle containing at least one of nitrogen, oxygen, sulfur and selenium as a heteroatom, and most preferably a 5-membered or 6-membered heterocycle. Is.

Examples of the heterocycle represented by Z ₁ include azoles (tetrazole, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,3,4 -Oxadiazole, 1,3-thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazole, pyrrole, pyrazole, indazole), azaindenes (tetrazaindene, pentazaindene, triazaindene) , Azines (pyrimidine, triazine, pyrazine, pyridazine).

Examples of the heterocycle represented by Z ₂ include, for example, triazoles (1,2,4-triazole, benzotriazole, 1,2,3-triazole), indazole, benzimidazole, azaindenes (tetrazaindene). , Pentazaindene), and tetrazole.

The preferred substituents contained in the development inhibitors represented by formulas (X-1) and (X-2) are as follows.

That is, R ₇₇ group, R ₇₈ O- group, R ₇₇ S-
Group, R ₇₇ OCO— group, R ₇₇ OSO ₂ — group, halogen atom, cyano group, nitro group, R ₇₇ SO ₂ — group, R ₇₈ CO—
Group, R ₇₇ COO-group, R ₇₇ SO ₂ N (R ₇₈ ) -group, R ₇₈
N (R ₇₉ ) SO ₂ — group, R ₇₈ N (R ₇₉ ) CO— group, R ₇₇
C (R ₇₈ ) = N-group, R ₇₇ N (R ₇₈ ) -group, R ₇₈ CON
(R ₇₉ ) -group, R ₇₇ OCON (R ₇₈ ) -group, R ₇₈ N (R
₇₉₎ CON (R ₈₀₎ - it includes groups or R ₇₇ SO ₂ O- group. Here, R ₇₇ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₈ , R ₇₉ and R ₈₀ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. When two or more R ₇₇ , R ₇₈ , R ₇₉ and R ₈₀ are present in one molecule, they may be linked to form a ring (for example, a benzene ring).

Examples of the compound represented by the formula (X-1) include, for example, substituted or unsubstituted mercaptoazoles (eg 1-phenyl-5-mercaptotetrazole,
1-propyl-5-mercaptotetrazole, 1-butyl-5-mercaptotetrazole, 2-methylthio-5
-Mercapto-1,3,4-thiadiazole, 3-methyl-4-phenyl-5-mercapto-1,2,4-triazole, 1- (4-ethylcarbamoylphenyl)-
2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-
Mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-phenyl-5-mercapto-1,3
4-oxadiazole, 1- {3- (3-methylureido) phenyl} -5-mercaptotetrazole, 1-
(4-Nitrophenyl) -5-mercaptotetrazole, 5- (2-ethylhexanoylamino) -2-mercaptobenzimidazole), substituted or unsubstituted mercaptoazaindenes (eg 6-methyl-4-mercapto-1) , 3,3a, 7-Tetraazaindene, 4,
6-dimethyl-2-mercapto-1,3,3a, 7-tetraazaindene), a substituted or unsubstituted mercaptopyrimidine (for example, 2-mercaptopyrimidine, 2-
Mercapto-4-methyl-6-hydroxypyrimidine).

Examples of the heterocyclic compound capable of forming imino silver include substituted or unsubstituted triazoles (eg 1,2,4-triazole, benzotriazole,
5-methylbenzotriazole, 5-nitrobenzotriazole, 5-bromobenzotriazole, 5-n-butylbenzotriazole, 5,6-dimethylbenzotriazole), substituted or unsubstituted indazoles (eg indazole, 5-nitroindazole) , 3-nitroindazole, 3-chloro-5-nitroindazole), and substituted or unsubstituted benzimidazoles (for example, 5-nitrobenzimidazole and 5,6-dichlorobenzimidazole).

X is B in the general formulas (I) and (II).
After becoming a compound having a development inhibitory property, it undergoes a certain chemical reaction with a developer component and changes to a compound that has substantially no development inhibitory property or is significantly reduced. It may be one that does. Examples of the functional group that undergoes such a chemical reaction include an ester group, a carbonyl group, an imino group, an immonium group, a Michael addition accepting group, and an imide group.

Examples of such a deactivating type development inhibitor include, for example, US Pat.
0-218644, 60-221750, 60
No. 233650, or the development inhibitor residues described in No. 61-11743.

Of these, those having an ester group are particularly preferable. Specifically, for example, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5.
-Mercaptotetrazole, 1- (3-maleimidophenyl) -5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,
3,4-thiadiazole, 5-nitro-3-phenoxycarbonylimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 1- (4
-Benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole , 5-
Succinimidomethylbenzotriazole, 2- {4-
Succinimidophenyl} -5-mercapto-1,3,3
4-oxadiazole, 6-phenoxycarbonyl-2
-Mercaptobenzoxazole, 2- (1-methoxycarbonylethylthio) -5-mercapto-1,3,4
-Thiadiazole, 2-butoxycarbonylmethoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 2- (N-hexylcarbamoylmethoxycarbonylmethylthio) -5-mercapto-1,3
4-thiadiazole, 5-butoxycarbonylmethoxycarbonylbenzotriazole and the like can be mentioned.

Preferred as X are mercaptoazoles and benzotriazoles. As mercaptoazoles, mercaptotetrazoles, 5-mercapto-1,3,4-thiadiazoles and 5-mercapto-1,3,4-oxadiazoles are more preferable.

Most preferably X is 5-mercapto-
1,3,4-thiadiazoles.

In the general formulas (I) and (II), k is preferably 0, 1 or 2.

Among the compounds represented by the general formula (I), preferred compounds are the compounds represented by the formula (IA) shown below.

[0114]

[Chemical 44] In formula (IA), R ¹¹ , B, X, A, A ′ and k have the same meanings as those in formula (I).

In formula (IA), preferred R ¹¹ is R ¹⁴ —
N (R ¹⁶ ) CON (R ¹⁵ )-and R ¹⁴ OCON
(R ¹⁵⁾ - a and, R ^14, R ¹⁵ and R ¹⁶ have the same meanings as described above. Moreover, in formula (IA), preferable k is 0 or 1.

In the general formulas (I) and (II), A and A'are preferably hydrogen atoms.

In the general formula (II), Q ¹ is preferably-
^{N (R 28) -CO-Q} 2 - is represented by divalent amino group examples of Q ^2, an ether bond, a thioether bond,
Alkylene group, ethylene bond, imino bond, sulfonyl group, carbonyl group, arylene group, divalent heterocyclic group,
The group which combined these two or more is mentioned.

R ²⁸ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and may have a substituent. R ²⁸ is preferably a hydrogen atom.

R ^{21 in the} general formula (II) is preferably a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0 or more.

The number of ring members of the heterocycle containing Q ¹ is preferably a 5- to 7-membered ring, and among them, the compound represented by the formula (IIA) shown in Chemical formula 45 below is more preferable.

[0121]

[Chemical 45] In the formula (IIA), Q ² has the same meaning as described above, and R ²¹ , A, A ′, B, X and k have the same meaning as in the general formula (II).

When R ^{11 in the} formula (IA) is R ¹⁷ CONH—, the formula (IB) shown in the following formula 46 and the formula (IC) shown in the following formula 47 are preferable.

[0123]

[Chemical 46]

[0124]

[Chemical 47] In the formula, R ³⁴ and R ³⁵ each represent a substituent, n ′ represents an integer of 2 or more, m represents an integer of 1 to 5, and when m is 2 or more,
R ³⁵ may be the same or different.
A, A ′, B, X and k have the same meanings as those in formula (I).

As R ³⁴ and R ³⁵ , for example, those mentioned as the substituents of R ^{14 in} the general formula (I) can be mentioned. Further, these substituents may be further substituted.

In formula (IB), preferred R ³⁴ is a substituent having 5 to 30 carbon atoms, and n ′ is preferably 2 to 5. In formula (IC), R ³⁵ preferably has 5 to 30 carbon atoms.

In order to more specifically arrange the contents of the present invention, specific examples of the compounds represented by the general formulas (I) and (II) are shown in the following chemical formulas 48 to 81. The compounds usable in the present invention are It is not limited to these.

[0128]

[Chemical 48]

[0129]

[Chemical 49]

[0130]

[Chemical 50]

[0131]

[Chemical 51]

[0132]

[Chemical 52]

[0133]

[Chemical 53]

[0134]

[Chemical 54]

[0135]

[Chemical 55]

[0136]

[Chemical 56]

[0137]

[Chemical 57]

[0138]

[Chemical 58]

[0139]

[Chemical 59]

[0140]

[Chemical 60]

[0141]

[Chemical formula 61]

[0142]

[Chemical formula 62]

[0143]

[Chemical 63]

[0144]

[Chemical 64]

[0145]

[Chemical 65]

[0146]

[Chemical 66]

[0147]

[Chemical 67]

[0148]

[Chemical 68]

[0149]

[Chemical 69]

[0150]

[Chemical 70]

[0151]

[Chemical 71]

[0152]

[Chemical 72]

[0153]

[Chemical formula 73]

[0154]

[Chemical 74]

[0155]

[Chemical 75]

[0156]

[Chemical 76]

[0157]

[Chemical 77]

[0158]

[Chemical 78]

[0159]

[Chemical 79]

[0160]

[Chemical 80]

[0161]

[Chemical 81] The compounds represented by formulas (I) and (II) are described in JP-A-49-129536, JP-A-52-57828 and JP-A-52-57828.
-21044, 60-233642, 60-2
No. 33648, No. 61-18946, No. 61-156
043, 61-213847, 61-2301.
No. 35, No. 61-236549, No. 62-62352.
No. 62-103639, U.S. Pat. No. 3,379,
529, 3,620,746, 4,332,8
No. 28, No. 4,377, 634, No. 4,684, 60
It can be synthesized according to the method described in No. 4, etc.

When the compounds represented by formulas (I) and (II) are used in a multilayer color photographic light-sensitive material, a silver halide emulsion layer or a yellow filter layer adjacent to the emulsion layer, an antihalation layer, an intermediate layer or It is contained in at least one layer such as a protective layer, but is preferably contained in the silver halide emulsion layer or an intermediate layer adjacent to the emulsion layer.

The compounds of the present invention represented by the general formulas (I) and (II) are generally contained in the same layer or adjacent layers, though they vary depending on the properties of the silver halide photographic light-sensitive material to be applied, the purpose or the processing method. The amount is 1 to 10 ^-7 mol, preferably 3 x 10 1 mol, relative to 1 mol of silver halide present.
^{It is −2 to} 3 × 10 ⁻⁵ mol.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide color photograph having on a support at least one color-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color-sensitivity but different sensitivities. A photosensitive material, the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light. The layers are arranged in the order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side. However, even if the above installation order is reversed depending on the purpose,
Further, the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer has a layer of JP-A-61-43748.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038 may contain a coupler and the like, and may contain a color mixing inhibitor as commonly used.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A No. 62-160448.
No. 63-89850, BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.
The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. .. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 μm or less, large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 1871
6 (November 1979), p. 648, ibid. 30710
5 (Nov. 1989), pp. 863-865, and "Graphics and Chemistry" by Graphide, published by P. Glafkides, Chemie et Phi.
sine Photographie, Paul
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin,
Photographic Emulsion Che
mistry (Focal Press, 196
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
l Press, 1964).

US Pat. Nos. 3,574,628 and 3,
665,394 and British Patent No. 1,413,748.
The monodisperse emulsions described in US Pat.

Also, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), Vol. 14, 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, ibid. 18716 and ibid.
No. 307105, the relevant parts are summarized in the table below.

The light-sensitive material of the present invention contains the grain size, grain size distribution, halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide emulsion inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± 40% of the average grain size). It is preferable that the particles have a particle size of

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide grain that is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that the fog is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 2 μm.

Fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains.

The silver coating amount of the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 page right column page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Page right column Page 868 5. Antifoggant page 24 to 25 page 649 page right column 868 to 870 page stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. Anti-staining agent Page 25 Right column Page 650 Left column to Page 872 Right column 8. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 page left column 873 to 874 page 11. Plasticizer, lubricant 27 pages 650 pages right column 876 pages 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 page right column 876-877 page Protective agent 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
It is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, as described in No. 52, regardless of the amount of developed silver produced by the development processing.

International Publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-2593
It is preferable to include the dye described in No. 58.

Various color couplers can be used in the light-sensitive material of the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-C to G,
And the same No. 307105, VII-C to G. Of these, the magenta coupler can be used in combination with the coupler of the present invention.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No.
17643, Item VII-G, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, section VII-F and ibid. 307105, VII-
Patents described in paragraph F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

R. D. No. 11449, 24241,
The bleaching accelerator releasing coupler described in JP-A No. 61-201247 is effective for shortening the processing time having a bleaching ability, and is particularly useful for a light-sensitive material using the tabular silver halide grains described above. When added, the effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-1576.
Nos. 38 and 59-170840 are preferable. Also, JP-A-60-107029 and JP-A-60-25
2340, JP-A-1-44940, and 1-4568.
Compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 7 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound releasing coupler, DIR coupler releasing coupler, European Patent No. 173,302A, No. 31
No. 3,308A, a coupler that releases a dye that recolors after separation, US Pat. No. 4,555,477, a ligand-releasing coupler, and a leuco dye-releasing coupler described in JP-A-63-75747. U.S. Patent No. 4,77
Examples thereof include couplers that release the fluorescent dye described in 4,181.

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

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-di-ethylpropyl) phthalate), phosphoric acid Or an ester of phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2) -Ethylhexylphenylphosphonate), benzoic acid esters (eg 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg N, N-). Ethyl dodecanamide, N, N-
Diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl) sebacate, Dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-ter).
t-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxy. Examples include ethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747.
272248, and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various antiseptics or antifungal agents such as 2- (4-thiazolyl) benzimidazole.

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid. 18
716, page 647, right column to page 648, left column, and the same No.
307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een, et al., Photographic Science and Engineering (Photogr. Sci. E)
ng. ), Vol. 19, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. in a color developing solution, 3 minutes 15 seconds processing 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling rate T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The photographic material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

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 a typical example thereof is 3-methyl-4-amino-.
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Mention may be made of N-ethyl-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It is common to include development inhibitors or antifoggants such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Various chelating agents represented by viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid. , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-dicarboxylic acid Representative examples thereof include (o-hydroxyphenylacetic acid) and salts thereof.

Next, the processing solutions and processing steps for the color light-sensitive material of the present invention will be described.

Among the processing steps of the color reversal photosensitive material of the present invention, the steps from black development to color development are as follows.

1) Black-white development-washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all US patents. Fourth,
In place of the rinse process described in No. 804,616, it is possible to simplify the process and reduce waste liquid.

4) Color development-adjustment-bleaching-fixing-washing-stable 5) Coloring development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development Development-washing-bleaching-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleaching fixing-washing-stable 10) Color development-bleaching-bleaching fixing-fixing- Washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleach-fixing-washing-stable 13) Coloring development-washing-bleach-fixing-washing-stable 14) Color development-bleach-fixing -Washing-Stable 15) Color development-Fixing-Bleach-fixing-Water washing-Stable In the processing steps of 4) to 15), the washing step immediately before the stabilizing step may be removed, or conversely, the stabilizing step of the final step is It does not have to be done. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described.

Known developing agents can be used in the black and white developing solution used in the present invention. As a developing agent,
Dihydroxybenzenes (eg hydroquinone),
3-Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid and U.S. Pat. No. 4,067,8.
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 72 can be used alone or in combination.

The black-and-white developing solution used in the present invention may further contain a preservative (eg, sulfite, bisulfite) if necessary.
Buffering agents (eg carbonate, boric acid, borate, alkanolamine), alkaline agents (eg hydroxide, carbonate), dissolving tablets (eg polyethylene glycols, their esters), pH adjusters (eg organic such as acetic acid) Acid), a sensitizer (for example, a quaternary ammonium salt), a development accelerator, a surfactant, an antifoaming agent, a film hardener, a viscosity imparting agent and the like.

The black-and-white developing solution used in the present invention must contain a compound acting as a silver halide solvent.
The sulfite, which is usually added as a preservative, plays the role. The sulfite and other silver halide solvents that can be used are specifically KSCN, NaSCN, K
₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂ O
₅ , K ₂ S ₂ O ₃ , Na ₂ S ₂ O _{3 and the} like can be mentioned.

The pH value of the developer thus adjusted is selected to an extent sufficient to give a desired density and contrast, but is in the range of about 8.5 to about 11.5.

In order to carry out the sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about three times as much as the standard process. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be shortened.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank.

The contact area between the photographic processing liquid and air in the processing tank can be expressed by the aperture ratio defined below.

That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably It is preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The reversal bath used after black and white development may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
Instead of the reversal bath, a light reversal treatment by re-exposure may be performed, and the reversal step may be omitted by adding the fogging agent to the color developing solution.

The silver halide color photographic light-sensitive material of the present invention is subjected to bleaching treatment or bleach-fixing treatment after color development. These treatments may be carried out immediately after the color development without passing through other processing steps, in order to prevent unnecessary post-development and air fog, and to reduce the carry-in of the color developing solution to the desilvering process. In addition, in order to wash out and detoxify the sensitizing dyes and dyes contained in the photographic light-sensitive material and the color-developing agent impregnated in the photographic light-sensitive material, stop, adjust, and wash with water after color development processing. A bleaching treatment or a bleach-fixing treatment may be carried out after the treatment steps such as.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. Can be used. Of these, aminodicarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are included.
II) Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. No. 17129 (July 1978), a compound having a mercapto group or a disulfide group;
Thiazolidine derivatives described in 0-140129; JP-B-45-8506, JP-A-52-20832, and JP-A-5-20832.
3-32735 and thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715.
And iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patents 966,410 and 2,748,430; JP-B-45-88.
No. 36 polyamine compound; Others, JP-A-49-4
0,943, 49-59,644, 53-9
4,927, 54-35,727, 55-2.
Compounds described in Nos. 6,506 and 58-163,940; bromide ions can 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, US Pat. No. 3,893,858.
, West German Patent No. 1,290,812, JP-A-53-9
The compounds described in 5,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 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 photographing.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is a compound of 2 to 5, and specifically, acetic acid, propionic acid and hydroxyacetic acid are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, it is also preferable to use a combination of thiosulfate, thiocyanate, thioether compound and thiourea. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to improve the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect or eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is
of the Society of Motion
Picture and Television E
nginers 64, P.N. 248-253 (1
May 955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. In addition, JP-A-57-8,5
No. 42, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, "Sterilization, sterilization and antifungal technology of microorganisms" edited by Sanitary Technology Association (1982) Industrial Technology Association, "Antibacterial and Antifungal Encyclopedia" edited by Japan Society for Antibacterial and Antifungal (19)
It is also possible to use the fungicide described in 1986).

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C. is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The 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, indoaniline compounds described in U.S. Pat. No. 3,342,597, and No. 3,342,59.
No. 9, Research Disclosure No. 14,850
And Schiff base type compounds described in 15, 1559,
Aldol compounds described in US Pat. No. 3,924, US Pat.
Metal salt complexes described in 719, 492, JP-A-53-13.
The urethane type compound described in No. 5628 can be mentioned.

The 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 described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

Various treatment solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0242]

【Example】

(Embodiment 1) Hereinafter, the present invention will be specifically described with reference to embodiments, but the present invention is not limited thereto. Preparation of Sample 101 A multilayer color light-sensitive material having each of the following compositions was prepared on a 127 μm-thick cellulose triacetate film support which was undercoated to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

Various additives constituting each layer are listed in Chemical Formulas 82 to 95 below.

The properties of the silver iodobromide emulsions (Emulsion A to Emulsion N) added to each layer are shown in Table 1 below.
The spectral sensitivities thereof are shown in Table 2 below, and the spectral sensitivities of the same emulsions K to N are shown in Table 3 below.

[0245]

[Chemical formula 82]

[0246]

[Chemical 83]

[0247]

[Chemical 84]

[0248]

[Chemical 85]

[0249]

[Chemical formula 86]

[0250]

[Chemical 87]

[0251]

[Chemical 88]

[0252]

[Chemical 89]

[0253]

[Chemical 90]

[0254]

[Chemical Formula 91]

[0255]

[Chemical Formula 92]

[0256]

[Chemical formula 93]

[0257]

[Chemical 94]

[0258]

[Chemical 95]

[0259]

[Table 1]

[0260]

[Table 2]

[0261]

[Table 3] (Composition of photosensitive layer) First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-40 0.1 g High boiling organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Gelatin 0.40 g High boiling organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Fine grained silver iodobromide emulsion with a fogged surface and inside (average grain size 0.06 μm, variation coefficient 18%, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-3 0.05 g Coupler C-9 0.05 g High boiling point organic solvent Oi1-2 0.1 g Additive P-1 0.1 g Fifth layer: medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0. 8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: High Sensitive red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g 7th layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg UV absorber U-1 0.01 g UV absorber U-2 0.002 g UV Absorbent U-5 0.01 g Dye D-1 0.02 g High boiling point organic solvent Oil-1 0.02 g Layer: intermediate layer Silver iodobromide emulsion whose surface and inside are fogged (average grain size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 1.0 g Additive P −1 0.2 g Anti-color mixing agent Cpd-A 0.1 g 9th layer: Low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-4 0.3 g Coupler C-7 0.05 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd -G 0.02 g High-boiling point organic solvent Oil-1 0.1 g High-boiling point organic solvent Oil-2 0.1 g 10th layer: Medium sensitivity green sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0 .1 g gelatine 0.6 g coupler C-4 0. g Coupler C-7 0.3 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-D 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g High boiling point organic solvent Oil- 2 0.01 g 11th layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.4 g Coupler C-7 0.1 g Compound Cpd-B 0.08 g Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-G 0.02g High boiling point organic solvent Oil-1 0.02g High boiling point organic solvent Oil-2 0.02g 12th Layer: Intermediate layer Gelatin 0.6 g Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 14th layer: intermediate layer gelatin 0.6 g 15th layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0. 2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g High boiling organic Solvent Oil-4 0.08 g 16th layer: Medium-speed blue-sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-10 0.1 g High boiling point organic solvent Oil-4 0.02 g 17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-50 .3 g Coupler C-6 0.6 g Coupler C-10 0.1 g High boiling organic solvent Oil-4 0.02 g 18th layer: 1st protective layer Gelatin 0.7 g Ultraviolet absorber U-1 0.2 g Ultraviolet absorber U-2 0.05 g Ultraviolet absorber U-5 0. 3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g 19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) silver amount 0.1 g gelatin 0.4 g 20th layer: third protective layer gelatin 0.4 g polymethylmethacrylate (average grain Diameter 1.5 μm) 0.1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Interface Activator W-2 0.03 g Also, The emulsion layer of all additives in addition to the composition F-
1-F-8 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer.

Further, as antiseptic and antifungal agents, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-benzoic acid butyl ester were added. (Preparation of Samples 102 to 108) In Sample 101, the compound of the present invention represented by the general formula (M) was used in place of the couplers added to the ninth layer, the tenth layer and the eleventh layer as shown in Table 4 below.
Samples 102 to 1 in the same manner except that they were added as shown in FIG.
08 was produced. (Preparation of Sample 109) In Sample 101, the compound I- (1) of the present invention represented by the general formula (I) was used as m ^{2 in} the second layer, the fourth layer, the seventh layer, the ninth layer and the eleventh layer. Sample 109 was prepared in the same manner except that 5 mg was added per unit. (Preparation of Samples 110 to 121) In Sample 109, instead of the couplers added to the ninth, tenth and eleventh layers, the compound of the present invention represented by the general formula (M) was used in Table 4 below.
The second layer, the fourth layer, the seventh layer
Compound I- of the present invention added to the layers, 9th and 11th layers
Samples 110 to 121 were prepared in the same manner except that the compounds of the present invention represented by the general formulas (I) and (II) were added instead of (1) as shown in Table 4 below.

[0263]

[Table 4] The maximum absorption wavelengths of the magenta couplers of the present invention used in the preparation of Samples 101 to 121 are shown in Table 5 below. M-
The difference between the maximum absorption wavelengths when 1 and M-2 are combined and when M-40 and M-57 are combined is 5 nm or less, and the other combinations are 5 nm or more.

[0264]

[Table 5] 35 mm for the samples 101 to 121 produced in this way
It was processed into a size patrone form and a practical shooting was performed. The subject was subjected to the following development processing using a color checker manufactured by Macbeth. The color reproducibility of the obtained practical sample was evaluated by a plurality of evaluators in five stages. The average value of the evaluation values is shown in comparison with Table 6 below as a value representing the color reproducibility.

[0265]

[Table 6] As is clear from Table 6 above, the light-sensitive material of the present invention is particularly excellent in color reproducibility. (Development processing) Processing time Time First development 6 minutes 38 ℃ Washing with water 2 minutes 38 ℃ Reversal 2 minutes 38 ℃ Color development 6 minutes 38 ℃ Adjustment 2 minutes 38 ℃ Bleach 6 minutes 38 ℃ Fixing 4 minutes 38 ℃ Washing with water 4 minutes 38 ℃ Stability 1 minute 25 ℃ The composition of each treatment solution was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 15 g Sodium bicarbonate 12 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Diethylene glycol 13 g Water was added. 1000 ml pH 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide. [Reversal liquid] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 3.0 g Stannous chloride / dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide. [Color developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate / dihydrate 36 g Potassium bromide 1.0 g Sodium iodide 90 mg Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6-dithiaoctane -1,8-diol 1.0g Water was added and 1000 ml pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide. [Preparation liquid] Ethylenediamine tetraacetic acid / disodium salt / dihydrate 8.0 g Sodium sulfite 12 g 1-thioglycerol 0.4 g Formaldehyde sodium bisulfite adduct 30 g Water added 1000 ml pH 6.20 pH is hydrochloric acid Or adjusted with sodium hydroxide. [Bleaching solution] Ethylenediamine tetraacetic acid / disodium salt / dihydrate 2.0 g Ethylenediamine tetraacetic acid / Fe (III) / ammonium / dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water 1000 ml pH 5 The pH of 70 was adjusted with hydrochloric acid or sodium hydroxide. [Fixer] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia. [Stabilizer] Benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water was added to 1000 ml pH 7.0 (Example 2) Example 1 The edge effect was measured about the samples 101-121 produced by. The edge effect was obtained by exposing the sample with a soft X-ray through a slit having a line width of 1 mm and 20 μm, followed by developing treatment in the same manner as in Example 1, measuring with a micro densitometer through a green filter, and taking a ratio of 20 μm / 1 mm. The value of the Etsuji effect was used. The results are shown in Table 7 below. In Table 7, the larger the value, the better.

[0266]

[Table 7] From Table 7 above, it can be seen that the light-sensitive material of the present invention has a large edge effect and is excellent in sharpness. (Example 3) color photographic material of Example 1 described in JP-A-1-158431, compounds of the present invention I- a (1) m ² per 10mg were added to the second layer, the seventh layer JP-A-1-Except that magenta couplers ExM-1, 2 were replaced with couplers M-2, M-57 of the present invention in equimolar amounts.
Sample 301 was prepared in the same manner as the color photographic light-sensitive material of Example 1 described in JP-A-158431. When the sample 301 was tested in the same manner as in Example 1, the same effects as in Example 1 were obtained, which was preferable.

[0267]

According to the present invention, a silver halide color photographic light-sensitive material having excellent color reproducibility and sharpness can be obtained.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one blue-sensitive layer, green-sensitive layer and red-sensitive layer on a support, wherein the green-sensitive layer is represented by the general formula (M Among the magenta dye-forming couplers represented by the formula (1), at least two couplers differing in the maximum absorption wavelength of color by 5 nm or more, and at least one layer constituting the light-sensitive material has the general formula (I) shown below.
Alternatively, a silver halide color photographic light-sensitive material containing at least one compound represented by the general formula (II) shown in Chemical formula 3 below. [Chemical 1] [Chemical 2] [Chemical 3] In the general formula (M), R ₁ and R ₂ each represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group which leaves upon reaction with an oxidized product of a developing agent. In the general formula (I), R ₁₁ is R ₁₄ —N (R ₁₆ ) CON (R ₁₅ ) —, R
₁₄ OCON (R ₁₅ )-, R ₁₄ SO ₂ N (R ₁₅ )-, R _{14
-N (R 16) SO 2 N} (R 15) - or R ₁₇ CONH-
Represents. Here, R ₁₄ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R _14
15 and R ₁₆ represent a hydrogen atom, an alkyl group or an aryl group, and R ₁₇ represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom. Alternatively, it represents a heterocyclic group. R ₁₂ and R ₁₃ represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0.3 or less, B represents a group which releases X after being separated from the hydroquinone mother nucleic acid product, and X represents a development inhibitor. And k represents an integer, and A and A ′ represent a hydrogen atom or a group capable of being removed with an alkali. In the general formula (II), Q ¹ represents at least one heteroatom, represents an atomic group necessary for forming a 5- or more-membered heterocyclic ring with a carbon atom to be bonded, and R ²¹ is substituted with a hydroquinone nucleus. Representing possible groups, B, X, k, A and A ′ have the same meanings as described in the general formula (I).