JPH0566577B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a precursor of a photographic chemical, and more particularly to a silver halide color photographic light-sensitive material containing a precursor of a color developing agent. [Prior Art] Photographic chemicals are generally used by being added to a light-sensitive material or contained in a photographic processing solution, depending on the purpose. Recently, for the purpose of simplifying the processing steps and speeding up the processing, attempts have often been made to add or blend specific photographic processing agents, such as color developing agents, into light-sensitive materials. In this way, the method of adding and blending a photographic processing agent into a light-sensitive material has the advantage of simplifying processing by reducing the amount of components contained in the processing solution. For this reason, the developer components may include components that cannot withstand storage, components that are difficult to use because they are reactive with other chemicals in the developer, or components that are difficult to dissolve in the developer at the required concentration. It is a very effective method to add these components to the photosensitive material in advance to make it usable. However, in order for each chemical added to a photosensitive material to exhibit its effect in a timely manner,
It is necessary to consider in advance which layer of the photosensitive material it should be added to, and in this case, it is desirable that each added chemical be non-diffusible within the layer and chemically stable. . This is particularly required when the chemical added to the photosensitive material is a precursor of an aromatic primary amine developing agent. Among the above-mentioned problems, the present invention particularly relates to the stabilization of chemicals added to constituent layers of light-sensitive materials, and more specifically, to the stabilization of precursors of aromatic primary amine color developing agents. . Many of the above-mentioned aromatic primary amine developing agents or their precursors are chemically active and easily oxidized in the atmosphere, and sometimes easily react with silver halides, causing desensitization, contamination, etc. The compound may have various problems, such as being difficult to use as it is, or its molecules are not large enough to provide diffusion resistance, causing the compound to diffuse into other layers. It has the disadvantage that it cannot be used easily. To this end, attempts have been made to select compounds with practically excellent performance or to research improved addition methods. As a result, several methods have become known for stably incorporating color developing agents into light-sensitive materials. In other words, a reaction product between a color developing agent and a metal salt is covered by the U.S. patent.
No. 3719492, etc., and salt formations of color developing agents and acids are disclosed in U.S. Patent No. 3764328 and JP-A-56
−6235, No. 56-16133, No. 56-54430, No. 56
−67842, No. 56-59232, No. 56-81837, No.
No. 56-83734, No. 56-83735, No. 56-83736,
No. 56-89735, No. 58-200233, etc., and the color developing agent Schiffbase is patented in the United States.
No. 2507114, No. 3342599, JP-A-54-9924, No.
No. 56-106241, No. 56-107236, No. 58-192031
No. 59-13239, etc., and amide and imide types of color developing agents are disclosed in U.S. Patent No. 803783.
No. 1069061, British Patent No. 1069061, Research Disclosure No. 12146, etc., and a color developing agent in which the nitrogen atom is protected with a substituted alkyl is disclosed in West German Patent No. 1159758, Research Disclosure No. 1200679, etc. Research Disclosure No. 13924, US Patent
2695234, etc., and the urethane type is disclosed in U.S. Pat.
14672, JP-A No. 57-76543, JP-A No. 57-179842,
No. 58-1139, No. 58-1140, No. 58-95344, etc., and the indoaniline type is described in U.S. Pat. Color developing agent precursors are described in JP-A-59-81643 and other publications. [Problems to be Solved by the Invention] The reaction product of the color developing agent and the metal salt is poorly soluble and difficult to add to the light-sensitive material, and sufficient color development cannot be obtained during development. Although the salt formed by the base drug and acid has good color development, there are problems such as desensitization and staining during raw storage, and the above-mentioned Schiff-based type tends to cause desensitization of the emulsion, and the Schiff-based color remains even after processing. In addition, the urethane type described above has disadvantages such as not being able to obtain sufficient coloring density, and
The above techniques have problems such as desensitization, fogging, staining, etc., occurring during storage, or insufficient color density during development. In particular, these aromatic primary amine developing agent precursors are mainly hydrolyzed by alkali to release the aromatic primary amine developing agent, so as mentioned above, the aromatic primary amine developing agent releasing property is The drawback is that it is difficult to satisfy storage stability at the same time. By the way, Japanese Patent Application Publication Nos. 54-145135 and 57-154234
No. 57-188035 and the like disclose couplers that release photographically useful groups, but aromatic primary amine developing agents are not described among these photographically useful groups. This seems to be due to the fact that the aromatic primary amine developing agent precursor inherently needs to release the aromatic primary amine developing agent in a non-imagewise manner. As a result of intensive research, it was possible to achieve a technology with a built-in aromatic primary amine developing agent precursor for silver halide color photographic light-sensitive materials by imagewise release of the aromatic primary amine developing agent. I found out what I can do. The present inventors have discovered, through molecular design, a compound that satisfies both the speed and storage stability of releasing an aromatic primary amine developing agent in an imagewise or non-imagewise manner, and have developed the silver halide color photographic light-sensitive material of the present invention. It has come to completion. That is, the present invention contains a stable aromatic primary amine developing agent precursor that does not cause desensitization, fogging, staining, etc. during manufacture and storage, and has a development accelerating effect during development and provides sufficient color density. In addition, our first technical objective is to provide a silver halide color photographic material containing a built-in aromatic primary amine developing agent precursor that can suppress the occurrence of fog while maintaining high sensitivity; To provide a silver halide color photographic material that can obtain high color density by processing with a developer (a developer containing a small amount of a color developing agent or an alkaline activator solution containing no color developing agent). is the second technical issue. [Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention which solves the above-mentioned technical problems comprises a photographic constituent layer including at least one light-sensitive silver halide emulsion layer on a support. In at least one of the photographic constituent layers, a silver halide color photographic light-sensitive material has a compound represented by the following general formula (1) (hereinafter referred to as a precursor of the color developing agent of the present invention or a precursor compound of the present invention). It is characterized by containing at least one of the following. General formula (1) COUP-J-CD In the formula, COUP represents a coupler component that can cause a coupling reaction with an oxidized color developing agent,
J represents a protecting group for CD that can release CD upon development, and CD is p- selected from compound group A below.
Represents a phenylenediamine color developing agent or its precursor. [Compound Group A] 4-amino-N,N-diethylaniline, 3-
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-(β
-methanesulfonamido)ethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-amino-N,N-diethylaniline, 3-methoxy-4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N,N-diethylaniline, 4-amino-N,
N-diethylaniline, N-ethyl-N-β-
[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-[β-methoxyethoxy]ethyl-3
-Methyl-4-aminoaniline In the color developing agent precursor of the present invention, the coupler component may bind -J-CD either at the coupling reaction active site or at any other position;
Preferably, -J-CD is bound at the coupling reaction active site. As used herein, the terms "coupler" and "coupler compound" refer to the coupler moiety, the entire compound containing the -J-CD group, respectively, and the term "coupler moiety" refers to It refers to the part excluding the -J-CD group. The present invention will be explained in detail below. First, general formula (1) will be explained. Coupler components represented by COUP include the following. Yellow coupler components include benzoylacetanilide couplers, pivaloylacetanilide couplers, malondianilide couplers, and the like. Examples of the magenta coupler component include 5-pyrazolone couplers, pyrazolinobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumarone couplers, and indazolone couplers. Cyan coupler components include phenol couplers, naphthol couplers, and the like. Colorless coupler components include indanone, malonic acid diester, imidazoline, oxazolidine, thiazolinone, and the like. The coupler component is usually monomeric, but may optionally form a dimer, oligomer, or part of a polymeric coupler component. Preferred coupler components in the present invention can be represented by the following general formulas (2), (3), (4), (5), (6), and (7). General formula (2)

[Formula] In the formula, R ₁ represents a tertiary alkyl group (e.g., pivaloyl group, etc.), a substituted or unsubstituted aryl group (e.g., phenyl group, naphthyl group, etc.), and R ₂ represents a hydrogen atom, a halogen atom (e.g., fluorine atom, etc.). , chlorine, bromine, etc.) or an alkoxy group (e.g., methoxy group, ethoxy group, etc.), and R ₃ represents a halogen atom (e.g., fluorine, chlorine, bromine, etc.), a hydroxy group, a nitro group, a cyano group, an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, undecyl group, etc.), cyanoalkyl group (e.g. cyanomethyl group, etc.), trifluoroalkyl group (e.g. trifluoromethyl group, etc.), aryl group (e.g. phenyl group, tolyl group, naphthyl group, etc.),
Alkyloxy groups (e.g. methoxy, benzyloxy, etc.), aryloxy groups (e.g. phenoxy, tolyloxy, etc.), hydroxycarbonyl groups, alkyloxycarbonyl groups (e.g. ethoxycarbonyl, dodecyloxycarbonyl, α-dodecyloxy) carbonylethoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), alkylacyloxy group (e.g., acetyloxy group, cyclohexycarbonyloxy group, etc.), arylacyloxy group (e.g., benzoyloxy group, etc.), alkyl Amino groups (e.g. ethylamino group, dimethylamino group, diethanolamino group, dodecylamino group, hexadecylamino group, etc.), arylamino groups (e.g. anilino group, naphthylamino group, etc.),
Alkylcarbamoyl group (e.g. ethylcarbamoyl group, carboxyethylcarbamoyl group, dodecylcarbamoyl group, 2,4-di-tert-amylphenoxybutylcarbamoyl group, etc.), arylcarbamoyl group (e.g. phenylcarbamoyl group, etc.), acylamino group (α(2,4-di-tert-amylphenoxy)hexanamide group, α(2,4
-di-tert-amylphenoxy)butanamide group, dodecanamide group, hexadecaneamide group,
Benzamide group, β-dodecylsulfonyl-α-
methylethanamide group, etc.), acyl group (e.g., benzoyl group, pentafluorobenzoyl group, ethylcarbonyl group, propylcarbonyl group, etc.), alkylthio group (e.g., methylthio group, propylthio group, octylthio group, dodecylthio group, etc.), alkylsulfonyl group ( For example, methylsulfonyl group,
ethylsulfonyl group, octylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group, etc.),
Alkylsulfamoyl groups (e.g. ethylsulfamoyl group, pentylsulfamoyl group, dodecylsulfamoyl group, N-methylsulfamoyl group, N,N-dimethylsulfamoyl group, etc.), alkylsulfonamide groups ( For example, it represents a methylsulfonamide group, an ethylsulfonamide group, a dodecylsulfonamide group, a p-dodecyl phenylsulfonamide group, etc., and n represents 1 or 2. General formula (3) In the formula, R ₄ represents an acylamino group, an anilino group, or a ureido group, each of which may have a substituent. Examples of the substituent include those represented by R ₃ above. R ₅ represents a phenyl group which may be substituted with the substituent represented by R ₃ above, and is preferably a halogen-substituted group. General formula (4) In the formula, R ₆ represents an alkyl group, an aralkyl group, or an aryl group which may be substituted with the substituent represented by R ₃ above, and R ₇ represents a halogen atom (for example, chlorine,
bromine atom), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, etc.), or a substituted or unsubstituted phenyl group. General formula (5) In the formula, R ₈ and R ₉ represent the same substituents as the group represented by R ₃ above, and n represents a positive integer of 1 to 3. General formula (6) In the formula, R ₁₀ represents the same substituent as the group represented by R ₃ above. General formula (7) In the formula, R ₁₁ represents the same substituent as R ₃ above. n
represents a positive integer from 1 to 3. Specific examples of yellow coupler components that can be used in the present invention include US Pat.
No. 3408194, No. 3551155, No. 3582322,
No. 3725072, No. 3891445, West German Patent No. 1547868,
West German Application No. 2219917, West German Application No. 2261361, West German Publication No.
No. 2414006, British Patent No. 1425020, Special Publication No. 1977-
No. 10783, JP-A-47-26133, JP-A No. 48-73147,
No. 51-102636, No. 50-6341, No. 50-123342
No. 50-130442, No. 51-21827, No. 50-
No. 87650, No. 52-82424, No. 52-115219, No. 58
Examples include those described in No.-95346. Specific examples of magenta coupler components include U.S. Patent No. 2600788, U.S. Patent No. 2983608, and U.S. Patent No. 3062653.
No. 3127269, No. 3311476, No. 3419391,
Same No. 3519429, No. 3558319, No. 3582322, Same No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 51-20826, No. 52-58922
No. 49-129538, No. 49-74027, No. 50-
No. 159336, No. 52-42121, No. 49-74028, No. 50
Examples include those described in Japanese Patent Application No. 55-110943, No. 60233, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 55-110943. Further, as specific examples of cyan coupler components, U.S. Pat.
No. 2474293, No. 2521908, No. 2895826, No.
No. 3034892, No. 3311476, No. 3458315, No.
No. 3476563, No. 3583971, No. 3591383, No. 3591383, No. 3583971, No. 3591383, No.
No. 3767411, No. 4004929, West German patent application (OLS)
No. 2414830, No. 2454329, JP-A-48-59838,
No. 51-26034, No. 48-5055, No. 51-146827,
Examples include those described in No. 52-69624, No. 52-90932, No. 58-95346, and the like. Next, in general formula (1), if J is bonded to a position other than the active site of the coupling reaction, an intramolecular nucleophilic reaction, an elimination reaction accompanied by electron transfer, or a hydrolysis reaction occurs to generate CD. Represents a releasable group. When J is bonded to the coupling reaction active site, J is -O-, -N-, -S-, -SO ₂ -, -C-
is a group of atoms substituted at the active site of the coupler component by
Contains a group that can release CD by causing an elimination reaction accompanied by electron transfer or a reaction such as hydrolysis reaction, or has an aldehyde group, and forms a Schiff base with a color developing agent. The color developing agent contains at least one type of group that has an anionic group or an anionic group that can form a salt with a color developing agent.
Among J in the precursor compound of the present invention, a preferable one is one that is bonded to the coupler at the coupling reaction active site of the coupler, causing a reaction such as an elimination reaction accompanied by electron transfer or a hydrolysis reaction to form CD.
Contains a group capable of releasing , or has an aldehyde group, and contains at least one group capable of forming a Schiff base with a color developing agent, or a group having an anionic group and capable of forming a salt with a color developing agent. It is particularly preferable that the group contains a group capable of releasing CD by causing a reaction such as an elimination reaction accompanied by electron transfer or a hydrolysis reaction. Note that the above intramolecular nucleophilic reaction, elimination reaction involving electron transfer, or hydrolysis reaction is covered by a U.S. patent.
No. 4248962, JP-A-57-15423, JP-A No. 57-188035
No. 58-98728, No. 53-29717, U.S. Patent
No. 4310612, Special Publication No. 14671, No. 14671, Publication No. 14671, No. 14671
No. 76543, No. 58-1139, No. 57-179842, etc., or U.S. Pat. No. 4,009,029, etc., and groups capable of forming a Schiff base with the above color developing agent are disclosed in U.S. Pat. Nos. 2,507,114 and 3,342,599. , JP-A No. 54-9924, etc., and the above-mentioned anionic group-containing group capable of forming a salt with a color developing agent is described in the patent specifications and publications listed in the salt-forming type section above. The present invention may also refer to these descriptions. When J is bonded to the coupling reaction active site, preferred examples of J are derivatives of the following substituents. -O-; For example, alkyloxy group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc. -N-; For example, alkylamino group, arylamino group, heterocyclic amino group, ring A heterocyclic group bonded with N in the middle, a sulfonamide group, an acylamino group,
Sulfonamide group etc. -S-; For example, arylthio group, alkylthio group, heterocyclic thio group, alkylcarbonylthio group, arylcarbonylthio group, alkylthiocarbonylthio group, arylaminothiocarbonylthio group, thiocarbonylthio group, carbonylthio group etc. -SO ₂ -; For example, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, etc. -C-; an alkyl aldehyde bis form, a benzaldehyde bis form, an isophthalaldehyde tetrakis form, a triphenylmethane compound, etc. Hereinafter, J is a coupling reaction The most preferred specific examples of J bonded to the active site will be listed, but the invention is not limited thereto. -O-;

【formula】

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【formula】

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【formula】

【formula】

【formula】

【formula】 -N-;

【formula】

【formula】

【formula】

【formula】

-S-;

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 【formula】

【formula】

[Formula] −SO ₂ −;

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 【formula】

【formula】

[Formula] The bond to J of CD is an unsubstituted amino group moiety, but it may be any other moiety, and in that case, the amino group having development activity can be converted into a precursor by using a protecting group. Regarding these, for example, the description in Research Disclosure (RD) No. 12924 can be referred to. The precursor compound of the present invention represented by the general formula (1) is illustrated below. The precursor compound of the present invention can be easily synthesized by conventionally known methods. The synthesis method is described in the patent specifications and publications of the above-mentioned couplers and in "Beilstein's Handbuch der origanische
Chemie” etc. Typical synthesis examples of the precursor compound represented by the general formula (1) of the present invention will be described below, but the present invention is not limited thereto. Synthesis Example 1 (Synthesis of Exemplary Compound (2)) 13 ml of trichloromethyl chloroformate was dissolved in 200 ml of ethyl acetate, and 46 g of 2-benzyloxycarbonylethylamide-4-[4 was added while keeping the internal temperature below 0°C. -hydroxymethyl-3-methyl-1-phenyl-5-pyrazolyloxy]-1-
A solution of 9 g of naphthol and pyridine dissolved in 200 ml of ethyl acetate is added dropwise. After dropping and reacting at the same temperature for 1 hour, a solution of 27 g of 3-methyl-N-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline dissolved in 200 ml of pyridine is added dropwise again at below 0°C. . After the dropwise addition, the reaction mixture was reacted at room temperature, purified by column chromatography, and hydrogenated in ethanol using Pd-C as a catalyst. The obtained compound is recrystallized from acetonitrile to obtain white crystals of the target compound. Yield 41g, mp.233℃~226℃, FD−
Mass: M ⁺ = 756, confirming that it was the target product. Synthesis Example 2 (Synthesis of Exemplified Compound (13)) 50g of 1-(2,3,4-trichlorophenyl)
-4-(3-benzyloxycarbonyl-4-hydroxy)phenylthio-3-[2-chloro-(5
-octadecenyl phthalimide)anilino]-5
- Pyrazolone was dissolved in 200ml dichloromethane and 5g of phosgene gas was dissolved under stirring at below 0℃.
Drop into 50ml of toluene. After dropping and reacting at room temperature, a solution of 15 g of 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamido)ethylaniline dissolved in 100 ml of pyridine was added dropwise and subjected to column chromatography. refine.
After hydrogenation in ethanol using Pd-C as a catalyst, the product is recrystallized from ethyl acetate to obtain white crystals of the desired product. Yield 35g, mp.186℃~190℃, FD−
Mass; M ⁺ = 1199, confirming that it was the target product. Above, the precursor of the color developing agent of the present invention in which J is bonded to the coupling reaction active site has been mainly described, but the present invention is not limited to this, and the present invention is not limited to this. nuclear reaction,
Including cases where it is a group that can release CD by causing an elimination reaction or hydrolysis reaction that involves electron transfer,
Among these, preferred is a group containing a group capable of releasing CD by causing an elimination reaction accompanied by electron transfer and a hydrolysis reaction. A concrete example of this is as follows. Example of withdrawal reaction involving electron transfer Example using hydrolysis reaction The amount of the precursor of the color developing agent of the present invention added is 0.001 to 0.001 to the total silver amount in the light-sensitive material per unit area.
It is preferably 200 mol%, more preferably 0.1 to 50 mol%. When the precursor of the color developing agent of the present invention is synthesized in a hydrophilic colloid solution, the precursor compound is maintained in a dispersed state in the hydrophilic colloid solution, so it can be used as is. However, if these compounds are in isolated form, hydrophilic organic solvents such as methyl alcohol,
Dissolve in ethyl alcohol or acetone, etc., and add and disperse in a hydrophilic colloid solution. Other dispersion methods include latex dispersion, methods using other polymers, and methods using coupler solvents such as tri-o-cresyl phosphate and dibutyl phthalate, which are used in oil-protected photosensitive materials. A method such as dispersing a precursor compound of the color developing agent of the invention in a hydrophilic colloid solution can be used. When dispersing these oil phases in an aqueous phase, commonly known anionic, nonionic, cationic, or other surfactants may be used. Hydrophilic colloids include gelatin, gelatin derivatives known as photographic binders, gelatin graft polymers,
Various cellulose derivatives, polyvinyl alcohol partial oxide, sodium alginate, poly-N-vinylpyrrolidone, etc. can be widely used. Various photographic antioxidants or stabilizers can also be added to these emulsions. More specifically, the method for incorporating the precursor of the color developing agent of the present invention into the silver halide emulsion or other photographic constituent layer coating solution according to the present invention will be described as follows.
When the precursor of the color developing agent of the present invention is alkali-soluble, it may be added as an alkaline solution, and when it is oil-soluble, it can be added, for example, in U.S. Pat. No. 2801171,
According to the method described in the specifications of 2272191 and 2304940, the precursor of the color developing agent of the present invention is dissolved in a high boiling point solvent, optionally with a low boiling point solvent, and then formed into fine particles. It is preferable to add it to the silver halide emulsion by dispersing it in the following manner. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. Also 2
It is also possible to use a mixture of more than one precursor of the color developing agent of the present invention. Further, in detail, the method of adding the precursor of the color developing agent of the present invention to the silver halide emulsion which is preferable in the present invention is as follows.
A species or two or more of the precursors of the color developing agent of the present invention are used together with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary, as well as organic acid amides, carbamates, esters, and ketones. , urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tri-cresyl phosphate, triphenyl phosphate,
Di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate,
N,N-di-ethyl-caprylamidobutyl,
N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl- G
High boiling point solvents such as o-chlorophenyl phosphate or fluorine paraffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol,
Dissolved in low boiling point solvents such as diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, and anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids. and/or mixed with an aqueous solution containing a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate and/or a hydrophilic binder such as gelatin, and mixed with a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc. It is emulsified and dispersed and added to a silver halide emulsion. In addition, the above-mentioned latex dispersion method and its effects are disclosed in JP-A Nos. 49-74538, 51-59943, and 54-
32552 publications and research disclosure
No. 14850, August 1976, pages 77-79. Suitable latexes include, for example, styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3
-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamide-
Homopolymers, copolymers and terpolymers of monomers such as 2-methylpropanesulfonic acid and the like. The precursor of the color developing agent of the present invention comprises a constituent layer provided on a support of a silver halide photographic light-sensitive material;
For example, it is contained in at least one layer such as a silver halide emulsion layer, an intermediate layer, a protective layer, and a subbing layer. Although it depends on the type of the precursor of the color developing agent, it is generally preferable to contain it in the silver halide emulsion layer or a layer adjacent thereto. The precursor compounds of the present invention incorporated into the light-sensitive material according to the present invention are chemically stable as long as they do not come into contact with the developer, and are compatible with silver halide and other various additives in the light-sensitive material. Since it has extremely low reactivity, it can be useful for improving the storage stability and photographic properties of light-sensitive materials, especially desensitization, fogging, and staining. As a method for processing the photographic material of the present invention, for example, a color developing solution containing a normal amount or a small amount of a color developing agent or an alkaline activator solution containing no color developing agent can be used. In addition, various other methods including bath treatment, such as a spray method in which the treatment liquid is atomized, or a wet method in which the treatment liquid is brought into contact with a carrier impregnated with the treatment liquid,
Alternatively, various processing methods such as a developing method using a viscous processing liquid can be used. The amount of color developing agent in the developer is 0.0001 mol/l to 0.1 mol/l.
is preferred. There are no particular limitations on the method of processing the photographic material of the present invention, and any processing method can be applied.
For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary, and a method in which bleaching and fixing are carried out separately after color development, followed by further washing with water if necessary. and/or methods of stabilizing; or prehardening, neutralization, color development, stop-fixing, washing, bleaching,
Method of fixing, washing with water, post hardening, washing with water, color development, washing with water, supplementary color development, stopping, bleaching, fixing,
Processing using any of the following methods: washing with water and stabilization in that order, or halogenation bleaching of the developed silver produced by color development, and then color development again to increase the amount of dye produced. You may. The color developing solution that may be used in processing the light-sensitive material of the present invention is an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or more, more preferably 9 to 12. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added. The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples. 4-amino-N,N-diethylaniline, 3-
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-β-hydroxyethylaniline, 3-methyl-
4-Amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl- N
-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-
N,N-dimethylaniline, N-ethyl-N-β
-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-
These include 3-methyl-4-aminoaniline and salts thereof such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, and the like. Furthermore, for example, JP-A-48-64932, JP-A No. 50-
No. 131526, No. 51-95849, and those described by Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951) are also mentioned as representative examples. Two or more of these aromatic primary amino compounds can be used in an appropriate combination depending on the purpose. For example, 3-methyl-4-amino-
N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, etc. may be used in any combination depending on the purpose. The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, Alkali metal halides, benzyl alcohol, water softeners,
A thickening agent, a development accelerator, etc. can also be optionally included. Examples of additives other than those mentioned above that are added to the color developer include bromides such as potassium bromide and ammonium bromide, alkali iodides, nitrobenzimidazole, mercaptobenzimidazole, and 5-benzimidazole.
Methyl-benzotriazole, 1-phenyl-5
- Compounds for rapid processing solutions such as mercaptotetrazole, as well as anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, etc. The photographic light-sensitive material of the present invention may be processed using an alkaline activator solution containing no color developing agent as well as using a color developing solution containing the above color developing agent. The activator solution is basically a commonly used color developer with the developing agent removed, and preferably has a pH in the range of about 7 to 14, particularly preferably in the range of 8 to 13. be. In addition, the treatment temperature with the activator liquid is 20
℃~70℃ is preferred, most preferred temperature is 30℃~
It is 60℃. As a buffer for the activator solution, known compounds such as sodium hydroxide and sodium carbonate can be used alone or in combination. Other additives such as antifoggants, development accelerators, water softeners, organic solvents, etc. can also be added to the alkaline activator solution. For details of the treatment with the alkaline activator solution, refer to the above description of the color developing solution. Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following. Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Ethyl etherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt Bleaching solution can be used with various additives along with the above bleaching agents. It may also contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. And, as in the case of the above-mentioned bleaching solution, various other additives such as pH buffers, optical brighteners, antifoaming agents, surfactants,
Preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained. The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned. The processing temperatures for various processing steps such as color development, bleach-fixing (or bleaching, fixing), washing with water, stabilization, drying, etc. performed as necessary for the silver halide color photographic light-sensitive material of the present invention are determined from the viewpoint of rapid processing. Preferably, it is carried out at a temperature of 30°C or higher. The silver halide color photographic material of the present invention is disclosed in JP-A-58-14834, JP-A-58-105145, and JP-A-58-58-1.
No. 134634 and No. 58-18631 and patent application No. 1983-
Stabilization treatment as an alternative to washing may be performed as shown in No. 2709 and No. 59-89288. The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye or a dye (AI dye) that decolorizes with a developer. Examples of the AI dye include oxonol dyes and hemioxonol dyes. , merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Examples of AI dyes that can be used include British Patent No. 584609;
1277429, JP 48-85130, JP 49-99620
No. 49-114420, No. 49-129537, No. 52-
No. 108115, No. 59-25845, No. 59-111640, No.
59-111641, U.S. Patent No. 2274782, U.S. Patent No. 2533472
No. 2956879, No. 3125448, No. 3148187,
No. 3177078, No. 3247127, No. 3260601, No. 3260601, No.
No. 3540887, No. 3575704, No. 3653905, No. 3540887, No. 3575704, No. 3653905, No.
Examples include those described in No. 3718472, No. 4071312, and No. 4070352. It is generally preferable to use these AI dyes in an amount of 2 x 10 ^-3 to 5 x 10 ^-1 mol, more preferably 1 x 10 ^-2 to 1 x 10 ^-1 mol, per mol of silver in the emulsion layer. The silver amount (silver deposition amount) in the silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention is not limited, but is set to 0.3 to 1 g/m ² in the entire photosensitive silver halide emulsion layer. is preferable. That is, in order to obtain excellent image quality, the silver amount is preferably 1 g/m ² or less, while in order to obtain high maximum density and high sensitivity, the silver amount is 0.3 g/m ² or more. It is preferable that Silver halide compositions preferably used in the present invention include silver bromide, silver chloride, silver chlorobromide, and silver chloroiodobromide. Furthermore, a mixture of these may also be used. In order to achieve fast developability, it is preferable that the halogen composition of the silver halide contains a chlorine atom, and silver chlorobromide or silver chloroiodobromide containing at least 1% silver chloride is particularly preferable. . Further, the crystals of these silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1.0.0] planes to [1.1.1] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. In addition, these silver halides are of the type that mainly forms latent images on the surface,
It may also be of a type formed inside the particles. Furthermore, tabular silver halide grains (see JP-A-58-113934 and Japanese Patent Application No. 59-170070) can also be used. Silver halide grains particularly preferably used in the present invention are substantially monodisperse, and may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method. Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the pH inside the reaction vessel,
For example, by controlling pAg, etc.,
It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains as described in No. 48521. Preferably, the silver halide grains used in the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion. These silver halide emulsions contain activated gelatin;
Sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers such as gold sensitizers. sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc. or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc. Specifically, ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadate (some of these act as sensitizers or fog suppressants depending on the amount) can be used alone or Chemical sensitization may be carried out by using appropriate combinations (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, the silver halide emulsion contains at least one hydroxytetrazaindene and a nitrogen-containing heterozygous compound having a mercapto group. It may contain at least one kind of ring compound. The silver halide used in the present invention contains an appropriate sensitizing dye at a rate of 5 x 10 ^-8 per mole of silver halide in order to impart photosensitivity in the desired wavelength range.
Optical sensitization may be achieved by adding up to 3×10 ⁻³ mol.
Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following. That is, as sensitizing dyes used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929080,
U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, No. 4025349, No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2945763, British Patent No. 505979, and the like. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2454629, No. 2776280, and the like. Furthermore, US Patent No. 2213995, US Patent No. 2493748
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2,519,001, West German Patent No. 929,080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. These sensitizing dyes may be used alone or in combination. The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary. Representative particularly preferred spectral sensitization methods include, for example, Japanese Patent Publications No. 43-4936, No. 43-22884, No. 45-4 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 18433, No. 47-37443, No. 48-28293, No. 49
-6209, 53-12375, JP-A-52-23931,
No. 52-51932, No. 54-80118, No. 58-153926
No. 59-116646, No. 59-116647, and the like. Further, regarding the combination of carbocyanine having a benzimidazole nucleus and other cyanine or merocyanine, for example, Japanese Patent Publication No. 45-25831;
47-11114, 47-25379, 48-38406
No. 48-38407, No. 54-34535, No. 55-1569
No., JP-A No. 50-33220, No. 50-38526, No. 51-
No. 107127, No. 51-115820, No. 51-135528, No.
Examples include No. 52-104916 and No. 52-104917. Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example,
No. 32753, No. 46-11627, JP-A No. 1483-1983, and Japanese Patent Publication No. 1483-1983 regarding merocyanine.
-38408, 48-41204, 50-40662, JP-A-56-25728, 58-10753, 58-91445
No. 59-116645, No. 50-33828, etc. In addition, regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication No. 43
-4932, 43-4933, 45-26470, 46
-18107, JP-A No. 47-8741, JP-A-59-114533, etc. Furthermore, the method described in JP-B-49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye is advantageous. It can be used for. In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone,
Dimethylformamide or Special Publication No. 50-40659
It is used by dissolving it in a hydrophilic organic solvent such as a fluorinated alcohol as described in the above. The additive may be added at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion. Each of the silver halide emulsion layers according to the present invention can contain a main coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye. As the main couplers that can be used in the present invention, yellow couplers, magenta couplers and cyan couplers can be used without any particular limitations. These main couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing coupler or the like in combination with these main couplers. The yellow couplers include open chain ketomethylene compounds, active point -o-aryl substituted couplers called so-called 2-equivalent type couplers, active point -o-acyl substituted couplers, active point hydantoin compound substituted couplers, and active point urazole compound substituted couplers. and active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -o-
Sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include US Pat. No. 2,875,057
No. 3265506, No. 3408194, No. 3551155,
3582322, 3725072, 3891445, West German Patent No. 1547868, West German Patent Application No. 2219917,
No. 2261361, No. 2414006, British Patent No. 1425020,
Special Publication No. 51-10783, Japanese Patent Publication No. 47-26133, No. 48-
No. 73147, No. 51-102636, No. 50-6341, No. 50
−123342, No. 50-130442, No. 51-21827,
No. 50-87650, No. 52-82424, No. 52-115219
No. 58-95346. Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. These magenta couplers are similar to the yellow couplers 4
Not only an equivalent type coupler but also a two-equivalent type coupler may be used. Specific examples of magenta couplers include U.S. Patent No. 2600788, U.S. Patent No. 2983608, and U.S. Patent No. 3062653.
No. 3127269, No. 3311476, No. 3419391,
Same No. 3519429, No. 3558319, No. 3582322, Same No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 51-20826, No. 52-58922
No. 49-129538, No. 49-74027, No. 50-
No. 159336, No. 52-42121, No. 49-74028, No. 50
Examples include those described in No. 60233, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 110943/1983. Furthermore, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Patent Nos. 2,369,929, 2,434,272, and
No. 2474293, No. 2521908, No. 2895826, No.
No. 3034892, No. 3311476, No. 3458315, No.
No. 3476563, No. 3583971, No. 3591383, No. 3591383, No. 3583971, No. 3591383, No.
No. 3767411, No. 4004929, West German patent application (OLS)
No. 2414830, No. 2454329, JP-A-48-59838,
No. 51-26034, No. 48-5055, No. 51-146827,
Examples include those described in No. 52-69624, No. 52-90932, No. 58-95346, and the like. Couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers, and diffusible DIR compounds may be used in combination in the silver halide emulsion layer of the present invention and other photographic constituent layers. Regarding non-diffusible DIR compounds, colored magenta or cyan couplers, a patent application filed by the present applicant in 1982-
For polymer couplers, reference may be made to the description in Japanese Patent Application No. 193611, filed by the present applicant in Japanese Patent Application No. 172151/1983. For the method of adding the main coupler that can be used in the present invention into the photographic constituent layer of the present invention, reference can be made to the method of adding the precursor compound of the present invention, and the amount added is not limited, but silver 1 1x per mole
10 ⁻³ to 5 mol is preferable, more preferably 1×
10 ⁻² to 5×510 ⁻¹ mol. The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as those published in Research Disclosure Magazine.
Antifoggants, stabilizers, as described in No. 17643;
Ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, and cellulose acetate. , polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc. Furthermore, ordinary transparent supports may be used, and these supports may be appropriately selected depending on the intended use of the photosensitive material. Ru. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Further, simultaneous coating of two or more layers by the methods described in US Pat. No. 2,761,791 and US Pat. No. 2,941,898 can also be used. In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. . Each of these photosensitive silver halide emulsion layers may consist of two or more layers. In the light-sensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and various layers such as a filter layer, anti-curl layer, protective layer, anti-halation layer, etc. may also be provided as constituent layers. They can be used in appropriate combinations. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included. [Effects of the Invention] The silver halide color photographic light-sensitive material of the present invention is characterized in that at least one of the photographic constituent layers contains a precursor of the color developing agent of the present invention. Contains the stable developing agent precursor of the present invention that does not cause desensitization, fogging, staining, etc. during storage, and has a development accelerating effect during development to obtain sufficient color density while maintaining high sensitivity. It exhibits effects such as being able to suppress the occurrence of fog. [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially applied from the support side to prepare silver halide color photographic light-sensitive material sample No. 1. Layer 1...1.2 g/m ² of gelatin, 0.32 g/m ² (in terms of silver, the same applies hereinafter) of blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol%), 0.50 g/m ² of dioctyl phthalate A layer containing 0.80 g/m ² of yellow coupler (Y-1) and Exemplified Compound 24 in an amount equivalent to 20 mol% of (Y-1). Layer 2...0.70g/ ^m2 gelatin, 12mg/ ^m2 anti-irradiation dye (AI-1), 6mg/ ^m2
An intermediate layer consisting of (AI-2). Layer 3...1.25 g/ ^m2 gelatin, 0.25 g/ ^m2 green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%),
0.62 g/m ² magenta coupler (M-1) dissolved in 0.30 g/m ² dioctyl phthalate
A layer containing. Layer 4: Intermediate layer consisting of 1.20 g/m ² of gelatin. Layer 5...1.20 g/m ² gelatin, 0.30 g/m ² red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%),
Layer containing 0.45 g/m ² cyan coupler (C-1) dissolved in 0.20 g/m ² dioctyl phthalate. Layer 6: Layer containing 0.30 g/m ² of ultraviolet absorber (UV-1) dissolved in 1.00 g/m ² of gelatin and 0.20 g/m ² of dioctyl phthalate. Layer 7: Layer containing 0.50 g/m ² of gelatin. In addition, as a hardening agent, 2,4-dichloro-6-
Sodium hydroxy-S-triazine layer 2,
4 and 7 in an amount of 0.017g per 1g of gelatin, respectively. (Y-1) (M-1) (C-1) (AI-1) (AI-2) (UV-1) Further, Sample No. 2 was prepared in the same manner as Sample No. 1, except that Exemplified Compound 24 in Layer 1 in Sample No. 1 was replaced with Exemplified Compound 30 in the same molar amount. Sample No. 3 was prepared in the same manner as Sample No. 1 except that Exemplified Compound 13 was added in an amount equivalent to 20 mol% of (M-1) together with (M-1) of layer 3 in Sample No. 1. . In the sample No. 1, 20 moles each of Exemplified Compound 24 together with (Y-1) in Layer 1, Exemplified Compound 28 together with (M-1) in Layer 3, and Exemplified Compound 9 together with (C-1) in Layer 5. Sample No. 4 was prepared in the same manner as Sample No. 1 above, except that an amount corresponding to % was added. Sample No. 1 was prepared in the same manner as Sample No. 1, except that 20 mol% of the following Comparative Compound A was added together with (Y-1), (M-1), and (C-1) in Sample No. 1. .5 was created. Sample No. 1 was prepared in the same manner as Sample No. 1, except that the following Comparative Compound B was added in an amount equivalent to 20 mol% each along with (Y-1), (M-1), and (C-1). .6 was created. Blank sample No. 7 was prepared in the same manner as sample No. 1 above, except that (Y-1), (M-1), and (C-1) were each increased by 20 mol% equivalent in sample No. 1. did. Comparative compound A (described in US Pat. No. 4,060,418) Comparative compound B (described in Japanese Patent Publication No. 58-14671) Each of the photosensitive material samples No. 1 to 7 was exposed to light through an optical wedge and MTF value measurement, and then processed in the following steps. Processing steps (38°C) Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing 1 minute Drying 60-80°C 2 minutes The composition of each processing solution is as follows. [Color developer] Pure water 800ml Benzyl alcohol 15ml Hydroxyamine sulfate 2.0g Potassium bromide 1.5g Sodium chloride 1.0g Potassium sulfite 2.0g Triethanolamine 2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl -4-aminoaniline sulfate
4.5g 1-hydroxyethylidene-1,1'-diphosphonic acid (60% aqueous solution) 1.5ml Potassium carbonate 32g Whitex BB (50% aqueous solution) (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) 2ml Add pure water to 1l and 20% potassium hydroxide or 10%
Adjust the pH to 11.0 with % dilute sulfuric acid. [Bleach-fix solution] Pure water 550ml Iron ammonium ethylenediaminetetraacetate 65g Ammonium thiosulfate 85g Sodium hydrogen sulfite 10g Sodium metabisulfite 2g Disodium ethylenediaminetetraacetic acid 20g Sodium bromide 10g Add pure water to make 1 liter, and add aqueous ammonia or dilute sulfuric acid. Adjust the pH to 7.0. Sensitometry was performed on each sample after the above treatment, and the maximum density (Dm), relative sensitivity, and fog (Fog) were determined. The results are shown in Table 1.

【table】

[Table] As is clear from the results in Table 1 above, Samples No. 1 to No. 4 using the compounds of the present invention are different from Samples No. 5 and No. 6 using compounds other than the present invention and the blank sample. No.
Since the sensitivity and maximum density are higher than that of No. 7, it can be seen that it is an excellent silver halide color photographic light-sensitive material with no contamination or desensitization during production or storage, and little fog despite having a development accelerating effect. . Example 2 Using the sample of Example 1, the same treatment as in Example 1 was carried out except that the amount of color developing agent in the developer was reduced to 1/2. Fog, sensitivity, and maximum density were calculated. The results are shown in Table 2.

[Table] As is clear from the results in Table 2 above, Samples No. 1 to No. 4 using the compound of the present invention are different from Comparative Sample No.
It is clear that compared to Sample No. 5, No. 6, and Blank Sample No. 7, even when the amount of color developing agent in the developer was reduced to half, high sensitivity and maximum density were still achieved and fog was low. This indicates that the silver halide color photographic light-sensitive material of the present invention has an excellent effect on special developers containing a small amount of developing agent and fluctuations in the concentration of the developing agent that may occur during processing. be. Example 3 After storing samples No. 1 to No. 7 of Example 1 at 60°C and 80% RH for 7 days, they were exposed to light, subjected to the treatment shown in Example 1, and subjected to sensitometry. and sensitivity were measured. Regarding the fog, an increased fog (ΔFog) was observed compared to the fog of each same-day developed sample (shown in Table 1 above). In addition, the sensitivity is calculated by multiplying the sensitivity of each sample (shown in Table 1 above) by 100.
We looked at the relative sensitivity. The results are shown in Table 3.

[Table] As is clear from the results in Table 3 above, samples No. 1 to No. 4 using the compound of the present invention are blank samples.
It can be seen that it maintains a high sensitivity comparable to No. 7, and also has less fogging. Example 4 A sample was prepared in the same manner as No. 1 except that exemplified compound 24 in layer 1 was removed and exemplified compound 31 was added to layer 2 in an amount equivalent to 20 moles of (Y-1). When the same treatment as in Example 1 was carried out, results substantially equivalent to those of Sample No. 1 were obtained in terms of fog, relative sensitivity, and maximum density. Comparative Example Regarding Sample No. 1 of Example 1, Exemplified Compound 24 in Layer 1 was replaced with an equimolar amount of Compound A (the structure is as shown below) which releases p-aminophenol and is shown in JP-A-54-145135. Comparative Sample A was prepared in the same manner as Sample No. 1 except for the above, and the same evaluation as in Example 1 was performed. The results are shown in Table 4.

[Table] As is clear from Table 4, Comparative Sample A using a compound other than the present invention had high fog, low relative sensitivity and low maximum density, and could not achieve the effects of the present invention. Compound A

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having a photographic constituent layer including at least one light-sensitive silver halide emulsion layer on a support, in which at least one of the photographic constituent layers contains the following: A silver halide color photographic material containing a compound represented by general formula (1). General formula (1) COUP-J-CD In the formula, COUP represents a coupler component that can cause a coupling reaction with an oxidized color developing agent,
J represents a protecting group for CD that can release CD upon development, and CD is p- selected from compound group A below.
Represents a phenylenediamine color developing agent or its precursor. [Compound Group A] 4-amino-N,N-diethylaniline, 3-
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-(β
-methanesulfonamido)ethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-amino-N,N-diethylaniline, 3-methoxy-4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N,N-diethylaniline, 4-amino-N,
N-diethylaniline, N-ethyl-N-β-
[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-[β-methoxyethoxy]ethyl-3
-Methyl-4-aminoaniline