JPH0549093B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic material, and more specifically, a silver halide photographic material containing a novel coupler capable of releasing a photographically useful group by a coupling reaction with an oxidized developer. It's about materials. [Prior art] As is well known, subtractive color photography uses aromatic
A grade amine color developing agent oxidatively couples the oxidation products of the color developing agent produced by reducing exposed silver halide grains with couplers that form yellow, cyan, and magenta dyes in a silver halide emulsion. A dye image is thereby formed. In these cases, as a yellow coupler to form a yellow dye, a compound having an open-chain active methylene group is generally used, and as a magenta coupler to form a magenta dye, a pyrazolone type, pyrazolotriazole type, or pyrazolone type is used. Compounds such as nobenzimidazole and indazolone are used, and phenol and naphthol compounds are used as cyan couplers to form cyan dyes. A coupler in which the reactive active sites are unsubstituted is called a 4-equivalent coupler, and stoichiometrically requires 4 moles of silver halide to form 1 mole of dye. On the other hand, a coupler whose reactive active site is substituted with a group that can leave without being oxidized is called a 2-equivalent coupler, which requires only 2 moles of silver halide to form 1 mole of dye, and has a low color-forming reaction rate. Various improvement effects are known, such as shortening of processing time and improvement of image sharpness by increasing sensitivity or thinning silver halide photographic materials. In addition, a photographically useful group (herein referred to as PUG) or its precursor is introduced into the reactive site of the coupler, and PUG is generated imagewise through a coupling reaction with an oxidized developer. A variety of compounds are known that emit. In recent years, image-wise release of various PUGs has become an important technology to achieve high sensitivity, high image quality, storage stability, etc. DIR (Development Inhibitor)
Releasing compounds suppress development in proportion to the amount of developed silver, and are therefore used to improve sharpness, graininess, etc. Examples of DIR compounds include US Pat. Nos. 3148062, 3227554, and 3617291;
No. 3,632,373, etc., but these compounds have various properties such as coupling reactivity, diffusivity, inhibitory properties, and storage stability that depend on inhibitors in which reactive active sites are substituted, so molecular design is difficult. It's difficult and I haven't found anything that satisfies everything yet. Recently, timing DIR compounds have been proposed in which the release of a development inhibitor is timed by an intramolecular nucleophilic reaction or an elimination reaction accompanied by electron transfer after a coupling reaction with an oxidized developer.
For example, US Patent No. 4248962, Japanese Patent Application Publication No. 53-29717
No. 54-145135, No. 57-154234, No. 57-
It is disclosed in No. 188035, No. 58-98728, etc. [Problems to be Solved by the Invention] The above-mentioned timing DIR compound can select a more preferable leaving group and protecting group for the inhibitor, so it has better coupling reactivity, storage stability, suppressability, etc. than the above-mentioned DIR compound. can be improved.
These timing DIR compounds are a technology that uses a timing group to slow down the release rate of the development inhibitor that controls the coupling reaction, but with conventional timing groups, the release rate of the development inhibitor after the coupling reaction is too fast. , the diffusivity is insufficient. That is, if a compound has practical coupling reactivity and storage stability, the release rate is too fast to dramatically improve the diffusibility. Additionally, JP-A-59-206834 and JP-A-59-206836 disclose timing DIR compounds in which the inhibitor is doubly protected; Since it is rate-limiting and the reaction does not necessarily require a first-stage coupling reaction, it is difficult to dramatically increase diffusivity, and it is unstable during storage. Therefore, when evaluating the effects of conventional timing DIR compounds on photographs, they are only effective at relatively high spatial frequencies. On the other hand, JP-A-57-150845, JP-A No. 59-50439,
U.S. Pat. No. 59-157638 and U.S. Pat. No. 59-170840 disclose couplers that release fogging agents imagewise, and U.S. Pat. No. 3,214,377 and U.S. Pat. No. 3,253,924
JP-A-51-17437 discloses a coupler that releases a dissolved physical development accelerator imagewise, and JP-A-57-138636 discloses a coupler that releases a developer. . However, since these PUG-releasing couplers act effectively only near the coupling reaction point, they have the disadvantage of emphasizing the strength and weakness of the concentration and worsening graininess. Therefore, the present invention is chemically stable and PUG
By using a novel compound that can adjust parameters such as release time, release rate, and diffusion rate and that can release PUG imagewise during development, it is possible to achieve excellent storage stability and sharpness. It has excellent image quality such as graininess and high sensitivity,
The first technical challenge is to be able to suppress the occurrence of fog, and if PUG is a group that suppresses development, the coupling reactivity is high.
The second technical problem is to make it possible to reduce the amount of PUG-emitting coupler used without reducing sensitivity by using the PUG-emitting coupler. [Means for Solving the Problems] The silver halide photographic material of the present invention that solves the above technical problems contains a compound represented by the following general formula (1) (hereinafter referred to as the PUG-emitting yellow coupler of the present invention). It is characterized by containing at least one kind. General formula (1) Y-O-D-J-PUG-B In the formula, Y represents a yellow coupler component that can cause a coupling reaction with an oxidized color developing agent to form a yellow dye, and D represents a phenylene group. In the formula, J represents a simple bond or a divalent organic group, B represents a protecting group for PUG that is bonded to PUG via a methylene group and can release PUG by a coupling reaction or a hydrolysis reaction, and PUG is -O-
DJ-PUG or PUG represents a photographically useful group. The reason why the silver halide photographic material using the PUG-emitting yellow coupler of the present invention represented by the general formula (1) above can solve the technical problems of the present invention is not necessarily clear, but the reason is as follows. It will be done. In other words, since it is doubly blocked and PUG is released in a two-step reaction, the diffusion distance is relatively long (diffusivity), and since two-step reactions are required for decomposition, the apparent It is thought that the activation energy for the above decomposition becomes higher (storage stability), and that the active site component can effectively increase the pKa of the coupler, so that the coupling reaction becomes faster (reactivity). By improving performance such as coupling reactivity, diffusivity, and storage stability, we can expect previously unimaginable synergistic effects such as storage stability, sensitivity, granularity, sharpness, etc. By combining these, it has become possible to achieve high sensitivity, high image quality, and high storage stability. As used herein, the terms "coupler" and "coupler compound" refer to a coupler moiety represented by Y, a joint group represented by -O-D-J-, a protecting group for PUG represented by B, and a PUG represented by B. refers to the entire compound containing the photographically useful group represented, and also refers to the "coupler component"
The term -O-D-
A joint group represented by J-, a joint group represented by B
It refers to the part of PUG from which the protecting group and the photographically useful group represented by PUG are removed, and is a group from which one hydrogen atom at the active site of a 4-equivalent coupler is removed. The present invention will be explained in detail below. First, general formula (1) will be explained. The yellow coupler component represented by Y includes benzoylacetanilide couplers, pivaloylacetanilide couplers, malondianilide couplers, and the like. The coupler component is usually monomeric, but may optionally form a dimer, oligomer, or part of a polymeric coupler component. A preferred coupler component in the present invention can be represented by the following general formula (2). General formula (2) 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, chlorine, etc.). _R3 represents a halogen atom (e.g. fluorine, chlorine, bromine, etc.), a hydroxy group, a nitro group, a cyano group, an alkyl group (e.g. a methyl group, ethyl group, propyl group, butyl group, dodecyl group, undecyl group, etc.), cyanoalkyl group (e.g. cyanomethyl group, cyanoethyl group, etc.), fluorinated alkyl group (e.g. fluorinated methyl group, fluorinated ethyl group, etc.), aryl groups (e.g., phenyl, tolyl, naphthyl, etc.), alkyloxy groups (e.g., methoxy, benzyloxy, etc.), aryloxy groups (e.g., phenoxy, tolyloxy, etc.), hydroxycarbonyl groups, alkyloxycarbonyl groups ( (e.g., ethoxycarbonyl group, dodecyloxycarbonyl group, α-dodecyloxycarbonyl ethoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), alkylacyloxy group (e.g., acetyloxy group, cyclohexylcarbonyloxy group, etc.) , arylacyloxy group (e.g. benzoyloxy group, etc.), alkylamino group (e.g. ethylamino group, dimethylamino group, diethanolamino group, dodecylamino group, hexadecylamino group, etc.), arylamino group (e.g. anilino group,
naphthylamino group, etc.), alkylcarbamoyl group (e.g. ethylcarbamoyl group, carboxyethylcarbamoyl group, dodecylcarbamoyl group,
2,4-di-tert-aminophenoxybutylcarbamoyl group, etc.), arylcarbamoyl group (e.g. phenylcarbamoyl group, etc.), acylamino group (α(2,4-di-tert-aminophenoxy)hexanamide group, α (2,4-di-tert-aminophenoxy)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 (e.g. methylsulfonyl group, ethylsulfonyl group,
octylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group), alkylsulfamoyl group (e.g. ethylsulfamoyl group, pentylsulfamoyl group, dodecylsulfamoyl group,
N-methylsulfamoyl group, N,N-dimethylsulfamoyl group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, ethylsulfonamide group, dodecylsulfonamide group, p-
dodecyl phenyl sulfonamide group, etc.), and n represents 1 or 2. Specific examples of yellow coupler components that can be used in the present invention include U.S. Pat.
No. 3265506, No. 3408194, No. 3551155, No.
No. 3582322, No. 3725072, No. 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. -DJ- is an atomic group substituted by -O- at the active site of the yellow coupler component, and PUG
The bond may have a strong bond that does not cleave under the development conditions, but in this case, according to the purpose of the present invention, it is necessary to use a low-molecular or It is preferable to have a hydrophilic group. Particularly preferably, after the coupling reaction, -O-D-J- undergoes an intramolecular nucleophilic reaction,
This is a group that can release PUG-B by causing an elimination reaction that involves electron transfer or by causing a reaction such as a hydrolysis reaction. The above intramolecular nucleophilic reaction, elimination reaction involving electron transfer, or hydrolysis reaction is covered by a US 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 US Pat. No. 4,009,029. Preferred examples of -O-D-J- are derivatives of the following substituents. -O-; For example, alkyloxy group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc. PUG is an oxygen atom or a nitrogen atom at the bonding position with -O-D-J- , refers to all molecules that have a sulfur atom and can be used in photography. Specific examples include development inhibitors, development accelerators, fogging agents, silver halide solvents, high boiling point solvents, hardeners, black and white developers, color developing agents, antioxidants, ultraviolet absorbers, dyes, couplers, etc. can be mentioned.
More preferably, it is a molecule having a nitrogen atom or a sulfur atom at the bonding position with -O-D-J-. B bonds to PUG via a methylene group and releases PUG through a coupling reaction, subsequent electron transfer reaction, hydrolysis reaction, intramolecular nucleophilic reaction, etc., or PUG through a hydrolysis reaction that does not require a coupling reaction. It is a protecting group for PUG that can release . In addition, B is due to the coupling reaction
When releasing PUG or -O-D-J-PUG, the rate of release of PUG by B is substantially higher than the release of -O-D-J-PUG from Y by controlling the timing group or the rate of the coupling reaction itself. Designed late. The PUG-emitting yellow coupler of the present invention represented by the general formula (1) needs to be made resistant to diffusion in order to be stably incorporated into a silver halide photographic light-sensitive material, but it is released by color development. It is preferable that the active site component as a whole is as hydrophilic as possible and diffusible. Although the PUG release mechanism of the present invention is not necessarily clear, the released PUG-
To explain the reaction caused by B using an example,
It can be considered as follows. [Coupling type] (QDI; oxidized color developing agent) [Hydrolyzable type] Next, the PUG of the present invention represented by the general formula (1)
Specific examples of emitting yellow couplers will be given, but the present invention is not limited thereto. [Exemplary compounds] (1) (2) (3) (Four) (Five) (6) (7) The PUG-emitting yellow coupler of the present invention can be synthesized by the following method. Synthesis method (method of introduction into the yellow coupler active site) (1) By reaction between the hydroxy form of the coupler active site and a halide. (2) Due to the reaction between the coupler active site halogen and phenols. In the above reaction, any solvent may be used, and if necessary, a base may be used. Regarding these synthesis methods, reference can be made to the methods described in the patent publications and patent specifications for 2-equivalent couplers cited in the yellow coupler component. Next, a synthesis example of the PUG-emitting yellow coupler of the present invention will be explained according to a reaction scheme. Synthesis example 1 (Synthesis of exemplified compound (2)) (1) Synthesis of the above compound (c) 50g of the above compound (a) and 20g of the above compound (b)
After dissolving in 500 ml of toluene and heating under reflux for 4 hours, toluene was distilled off under reduced pressure. Purify by column chromatography to obtain 30g of target product (c)
I got it. (2) Synthesis of the above compound (d) 30 g of the above compound (c) was dissolved in 300 ml of methylene chloride and added dropwise to a toluene solution in which 1.5 times the mole of phosgene gas had been dissolved. The reaction was carried out at room temperature for 5 hours, and the disappearance of the raw material was confirmed by TLC.The solvent was distilled off under reduced pressure and purified by column chromatography to obtain the pale yellow target product (caramel) (d). Obtained. (3) Synthesis of the above compound (f) The caramel compound (d) was dissolved in 200 ml of acetonitrile, and a solution of 15 g of the above compound (e) dissolved in 50 ml of pyridine was added dropwise at 0°C or lower. 1
After reacting at the same temperature for 4 hours, the reaction was carried out at room temperature, the solvent was distilled off, and the target product (caramel) (f) was purified by column chromatography (13 g).
I got it. The structure was confirmed with FD−Mass; M ⁺ =911. The other PUG-releasing yellow couplers of the present invention described above can also be easily synthesized according to the above synthesis method. Although the PUG-releasing yellow coupler of the present invention may be used alone, it is preferable to use it in combination with a normal photographic yellow coupler (hereinafter referred to as the main coupler), and the amount of the PUG-releasing yellow coupler of the present invention added is 1 per mole of the main coupler
×10 ⁻⁴ to 1 mol is preferable, more preferably 1×
10 ⁻³ to 0.1 mole. In addition, when the PUG-releasing yellow coupler of the present invention is used alone, the amount of the main coupler added below may be referred to. When the PUG-releasing yellow coupler of the present invention is synthesized in a hydrophilic colloid solution, the PUG-releasing yellow coupler is kept dispersed in the hydrophilic colloid solution and can be used as is. However, when these PUG-emitting yellow couplers are in an isolated state, they are dissolved in a hydrophilic organic solvent such as methyl alcohol, ethyl alcohol or acetone, and added to and dispersed in a hydrophilic colloid solution. Other dispersion methods include latex dispersion, methods using other polymers, and coupler solvents such as tri-o-cresyl phosphate and dibutyl phthalate used in oil-protected photosensitive materials. A method such as dispersing the PUG-releasing yellow coupler of the present 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 that can be widely used include gelatin, gelatin derivatives known as photographic binders, gelatin graft polymers, various cellulose derivatives, polyvinyl alcohol partial oxides, sodium alginate, and poly-N-vinylpyrrolidone. I can do it. Various photographic antioxidants or stabilizers can also be added to these emulsions. More specifically, the method of incorporating the PUG-releasing yellow coupler of the present invention into the silver halide emulsion or coating solution for other photographic constituent layers according to the present invention will be described in more detail. In some cases it may be added as an alkaline solution; in some cases it is oil-soluble;
For example, U.S. Patent Nos. 2322027, 2801170, 2801171, 2272191, and 2304940.
PUG of the present invention according to the method described in each specification of No.
It is preferable to dissolve the emitting yellow coupler in a high boiling point solvent, optionally in combination with a low boiling point solvent, and add the dispersion in the form of fine particles to the silver halide emulsion. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. Also, two or more types of PUG of the present invention
A mixture of emitting yellow couplers may be used. Furthermore, the PUG of the present invention preferred in the present invention
To describe in detail the method of adding a yellow emitting coupler to a silver halide emulsion, one or more of the PUG emitting yellow couplers of the present invention are optionally added to other main couplers, hydroquinone derivatives,
In addition to anti-fading agents and ultraviolet absorbers, organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-
n-Butyl phthalate, tricresyl 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-di -o-chlorophenyl phosphate or high boiling point solvent such as fluorine paraffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride,
Dissolved in a low boiling point solvent such as chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan sesquioleate and sorbitan. Mix with an aqueous solution containing a nonionic surfactant such as monolauric acid ester and/or a hydrophilic binder such as gelatin, emulsify and disperse with a high-speed rotation mixer, colloid mill, ultrasonic dispersion device, etc., and add to the silver halide emulsion. be done. In addition, the above-mentioned latex dispersion method and its effects are disclosed in JP-A-49-74538, JP-A-51-59943, and JP-A-54-54.
32552 publications and research disclosure
August 1976, No. 14850, 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-2
- Homopolymers, copolymers and terpolymers of monomers such as methylpropanesulfonic acid and the like. The PUG-emitting yellow coupler of the present invention is contained in at least one of the constituent layers provided on the support of a silver halide photographic light-sensitive material, such as a silver halide emulsion layer, an intermediate layer, a protective layer, and a subbing layer. It is something that forces you to do something. Although it depends on the type of the PUG-emitting yellow coupler, it is generally preferable to include it in the silver halide emulsion layer or a layer adjacent thereto. The PUG-emitting yellow coupler of the present invention incorporated into the photosensitive material according to the present invention is
As long as they do not come into contact with color developing agents, they are chemically stable and have extremely low reactivity with silver halide and other various additives in light-sensitive materials, so they have a significant impact on the storage stability and photographic properties of light-sensitive materials. This can be useful in improving the appearance, fog, staining, etc. As a method for processing the photographic material of the present invention, for example, a color developing bath containing a color developing agent can be used. In addition, various other methods such as bath processing, such as a spray method in which a processing liquid is atomized, a wet method in which contact is made with a carrier impregnated with a processing liquid, and a developing method using a viscous processing liquid, are also available. method can be used. 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. This aromatic primary amine developing agent as a color developing agent has a primary amine on the aromatic ring.
It is a compound having a grade amino group and capable of developing exposed silver halide, and a precursor for forming such a compound may be added if necessary. 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. The amount of these aromatic primary amino compounds to be used depends on where the activity of the developer is set; however, in order to increase the activity, it is preferable to increase the amount used. The amount used is 0.0002 mol/
It is used in the range from 0.7 mol/ to 0.7 mol/. Moreover, two or more compounds can be used in 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-
Combinations such as ethyl-N-β-hydroxyethylaniline can be freely used 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, thickeners, development accelerators, and the like may optionally be 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. 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 aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl etherdiaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic 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 bleaching solution mentioned above, 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. In the photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention, a water-soluble dye or a dye (AI dye) that decolorizes with a color development processing solution can be added.
The AI dyes include oxonol dyes, 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 the UK patent
No. 584609, No. 1277429, Unexamined Japanese Patent Publication No. 1977-85130, No.
No. 49-99620, No. 49-114420, No. 49-129537,
No. 52-108115, No. 59-25845, No. 59-111640
No. 59-111641, U.S. Patent No. 2274782, No. 59-111641, US Pat.
No. 2533472, No. 2956879, No. 3125448, No.
No. 3148187, No. 3177078, No. 3247127, No. 3148187, No. 3177078, No. 3247127, No.
No. 3260601, No. 3540887, No. 3575704, No. 3575704, No. 3540887, No. 3575704, No.
No. 3653905, No. 3718472, No. 4071312, No. 3653905, No. 3718472, No. 4071312, No.
Examples include those described in 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 preferably 0.3 g/m ²
It is preferable that it is above. 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 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, a method may be used in which seed particles are produced by an acidic method and further grown by an ammonia method, which has a high growth rate, to grow to a predetermined size. PH and pAg in the reaction vessel when growing silver halide grains
It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, for example, as described in JP-A-54-48521. 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 used in the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion containing at least one hydroxytetrazaindene and mercapto group is produced. It may contain at least one type of heterocyclic 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 examples of 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. In addition, regarding the combination of carbocyanine having a benzimidazole nucleus and other cyanine or merocyanine, for example, Japanese Patent Publication No. 25831/1983;
No. 47-11114, No. 47-25379, No. 48-38406,
No. 48-38407, No. 54-34535, No. 55-1569,
JP-A-50-33220, JP-A No. 50-38526, JP-A 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, 45-29470, 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 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 -o-acyl substituted couplers, active point substituted couplers with hydantoin compounds, active point substituted couplers with urazole compounds. 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. 3772002, No. 3933494, No.
No. 4004929, West German Patent Application (OLS) No. 2414830,
JP-A No. 2454329, JP-A-48-59838, JP-A No. 51-26034
No. 48-5055, No. 51-146827, No. 52-
Examples include those described in No. 69624, No. 52-90932, No. 58-95346, and Japanese Patent Publication No. 49-11572. The silver halide emulsion layer of the present invention and other photographic constituent layers contain non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers, and diffusible
A coupler such as a DIR compound may be used in combination. Regarding non-diffusible DIR compounds, colored magenta or cyan couplers, a patent application filed in 1983 by the applicant
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. The method of adding the main coupler that can be used in the present invention into the photographic constituent layer of the present invention is as follows.
You can refer to the method of adding PUG-emitting yellow coupler, and the amount added is not limited, but
The amount is preferably 1 x 10 ^-3 to 5 mol, more preferably 1 x 10 ^-2 to 5 x 10 ^-1 mol per mol of silver. The silver halide coupler 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] By using the PUG-releasing yellow coupler of the present invention, a photographically useful group (PUG) can be stably incorporated into a silver halide photographic light-sensitive material. Not only can we provide silver oxide photographic materials, but we can also release them imagewise.
When PUGs such as inhibitors, couplers, fogging agents, high boiling point solvents, silver halide solvents, and black and white developing agents are introduced, sharpness, graininess, sensitivity,
Factors related to image formation such as color reproduction can be improved, and when a hardening agent and the like are introduced as PUG, the physical properties of the film can be improved. When preservatives, antioxidants, ultraviolet absorbers, etc. are introduced as PUG, image storage stability after development can be improved. Furthermore, when PUG is a color developing agent, it has the effect of promoting development and reducing the amount of replenishment. Furthermore, if a highly reactive PUG-emitting yellow coupler of the present invention is used, the amount of PUG-emitting yellow coupler used can be reduced, and when the coupler is colored, high sensitivity can be achieved. In addition, the PUG-emitting yellow coupler of the present invention has high timing properties, so it can be effective relatively late in the development process or in the low spatial frequency region, which means that the PUG is effective during the development process. Even if it is a group that inhibits or interferes with color-forming reactions, it does not prevent development reactions or color-forming reactions, but prevents unnecessary reactions, resulting in high color development and sharpness, or high color development and low fog, etc. It is possible to achieve contradictory objectives simultaneously. Therefore, the silver halide photographic material of the present invention can achieve high sensitivity, high image quality, high storage stability, etc. [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 First, the effectiveness of using a DIR compound as PUG in the PUG-releasing yellow coupler of the present invention was tested. On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare silver halide color photographic material sample No. 1. Layer 1...1.2 g/m ² gelatin, 0.32 g/m ² (in terms of silver, the same applies hereinafter) blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol%), 0.50 g/m ² dioctyl Layer containing 0.80 g/m ² of yellow coupler (Y-1) and 0.5×10 ⁻⁵ mol/m ² of exemplary compound (2) dissolved in phthalate. Layer 2: Intermediate layer consisting of 0.70 g/m ² gelatin, 12 mg/m ² anti-irradiation dye (AI-1), and 6 mg/m ² (AI-2). Layer 3...1.25 g/m ² gelatin, 0.25 g/m ² green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%),
Dissolved in 0.30g/ ^m2 dioctyl phthalate
Layer containing 0.62 g/m ² of magenta coupler (M-1). 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%),
Dissolved in 0.20g/ ^m2 dioctyl phthalate
Layer containing 0.45 g/m ² of cyan coupler (C-1). 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: A layer containing 0.50 g/m ² of gelatin. In addition, as a hardening agent, 2,4-dichloro-6-
layer 2 of sodium hydroxy-S-triazine;
0.017 per gram of gelatin in 4 and 7, respectively.
g. (Y-1) (M-1) (C-1) (AI-1) (AI-2) (UV-1) In addition, the exemplary compound of layer 1 in sample No. 1
(2) and the same mole of exemplified compound (5) and the following comparative compound
Samples No. 2 to No. 4 were prepared in the same manner as Sample No. 1 except that (A) and (B) were replaced. Furthermore, a blank from which the DIR compound was removed was designated as sample No. 5. After each of the above photosensitive material test Nos. 1 to 5 was exposed through an optical wedge and MTF value measurement, it was processed in the following steps. Processing steps (38°C) Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing with water 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 1 and 20% potassium hydroxide or
Adjust the pH to 10.2 with 10% dilute sulfuric acid. [Bleach-fix solution] Pure water 550ml Iron()ammonium ethylenediaminetetraacetate
65 g Ammonium thiosulfate 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite 2 g Disodium ethylenediaminetetraacetic acid 20 g Sodium bromide 10 g Add pure water to make 1, and adjust to PH = 7.0 with aqueous ammonia or dilute sulfuric acid. Sensitometry was performed using blue light on each sample after the above treatment, and the maximum density (Dm) and fog (Fog) were determined. In addition, the MTF (Modulatio Transfer Function) of the blue-sensitive silver halide emulsion layer
was determined using a microdensitometer, and the MTF values at a spatial frequency of 5 lines/mm were compared. In addition, MTF
It is well known to those skilled in the art that the sharpness of an image is determined by
Photographic process 3rd edition". The results are shown in Table 1. Comparative compound (A) Comparative compound (B) [Both (A) and (B) described in JP-A-54-145135]

[Table] From the results shown in Table 1 above, Samples No. 1 to No. 4 using the DIR compound releasing coupler of the present invention, Sample No. 3 using the comparative DIR compound releasing coupler not according to the present invention, It is clear that compared to No. 4, the fog is rather low despite the high maximum density, and the MTF at low spatial frequencies is high.
Furthermore, compared to blank sample No. 5 that does not use DIR compounds, although the decrease in maximum concentration is small,
It can be seen that the MTF has been dramatically improved and fog has been reduced, indicating a high sharpness improvement effect. Example 2 A sample was prepared in the same manner as in Example 1, and subjected to the same normal treatment as in Example 1 and a treatment in which 0.5 ml of bleach-fix solution was added to the color developer of Example 1. The gamma (γ) of the 1.8 portion was compared to determine the processing variation (%). Relative sensitivity was also determined by setting the sensitivity of a blank containing nothing as 100. Processing variation (%) γ of bleach-fix solution containing process/normal process γ×
100 The results are shown in Table 2.

[Table] Generally, the bleach-fix solution mixes into the color developing solution during processing, causing the density to fluctuate, but it is known that inhibitors are effective in improving this processing variation. However, the use of an inhibitor also inhibits the development of silver halide, which tends to cause a decrease in sensitivity. This is shown in Table 2
This is also clear from the results of sample 12. On the other hand, the PUG-emitting yellow coupler of the present invention has a high timing function, so it is effective in the later stages of development, and it is found to be an excellent product that hardly causes a decrease in sensitivity while suppressing processing fluctuations. Comparative compound (C) Example 3 After storing samples No. 1 to No. 5 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 relative sensitivity were measured. Regarding the fog, an increased fog (ΔFog) was observed compared to the fog of each sample developed on the same day (shown in Table 1 above). Relative sensitivity (%) Sensitivity after raw storage / Sensitivity of same-day development ×
100 The results are shown in Table 3.

[Table] As is clear from Table 3 above, according to the present invention, it is possible to suppress the increase in fog, and moreover, it is possible to suppress the increase in fog caused by thermal decomposition.
It can be seen that due to the small amount of PUG emission, the sensitivity decreases little and the raw storage stability is as good as that of blank sample No. 5, which does not contain a built-in PUG emission yellow coupler. On the other hand, in samples No. 5 and No. 4 using comparative DIR-emitting couplers, the fog was reduced, but the sensitivity was also greatly reduced, indicating that PUG was released non-imagewise due to thermal decomposition. Comparative Example Sample 8 was prepared in the same manner as Sample No. 1 of Example 1, except that the exemplified compound (2) in layer 1 was replaced with the same mole of comparative compound (E). The same evaluation as in Example 3 was performed to evaluate the raw storage stability of the sample. The results are shown in the table.

[Table] Compounds listed in the upper right column of the page (6)
As is clear from 2 in Table 3, comparative compound (E)
Sample No. 8 containing . Example 4 2 x 10 ^-2 moles of yellow coupler (Y-2), exemplary compounds (3) and (7) of the present invention, and the following comparative couplers
(D) 4 × 10 ^-4 mol each and a blank containing only coupler (Y-2), tricresyl phosphate 15
This solution was mixed with 300 ml of a 5% aqueous gelatin solution containing 1.5 g of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont) and emulsified and dispersed in a colloid mill. A dispersion of this coupler was mixed with blue-sensitive silver iodobromide (silver iodide 6 mol%, silver iodide 6 mol%,
Mix 1 kg of a photographic emulsion containing 0.2 mol of silver bromide (94 mol%) and 40 g of gelatin, add 20 ml of a 2% solution of 1,2-bis(vinylsulfonyl)ethane as a hardening agent, and transfer it onto a cellulose triacetate film base. Coated and dried. Sample No. of a silver halide color photographic material with a gelatin protective layer coated on top of this layer.
15 to No. 18 were created. The amount of silver applied to each sample at this time was 1 g/m ² . After each of these samples was wedge exposed in a conventional manner, they were processed using the following processing steps and the processing solution composition shown below. Processing process (38℃) Color development 3 minutes 15 seconds Bleach fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds [Color developer composition] 4- Amino-3-ethyl-N-ethyl-N-(β
-hydroxyethyl)-aniline sulfate 4.75g Anhydrous potassium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 3.75g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1, and use potassium hydroxide to
Adjust to PH=10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1, and adjust the pH using ammonia water.
= 6.0. [Fixer composition] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1, and adjust to PH=6.0 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 ml Add water to make 1. The yellow dye image obtained above was measured with blue light using a densitometer (PD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.), and the color development sensitivity (relative value when the sensitivity in sample No. 18 was set as 100) was determined. ), fog and RMS granularity of the 0.5 density area (for example, described in "Chemistry of Photography" Shashin Kogyo Publishing Co., Ltd.) were measured using a circular aperture with a diameter of 48 μm, and sample No. 18
Table 4 shows the relative granularity expressed as 100. Note that the smaller the granularity value, the better the granularity. (Y-2) Comparative compound (D) (DIR coupler described in JP-A-54-145135)

[Table] From the results shown in Table 4 above, samples No. 15 to No. 16 using the DIR coupler of the present invention have higher sensitivity and less fog than sample No. 17 using the comparative compound (D).
Moreover, the effect of improving graininess is even higher. On the other hand, sample No. 18, which does not contain a DIR coupler, has high sensitivity but has large fog and extremely poor granularity, which clearly shows the improvement effect of the present invention. Sample 19 was prepared in the same manner as Sample No. 1 of Example 1, except that the exemplified compound (2) in layer 1 was replaced with the same mole of comparative compound (F), and then The same evaluation as in 3 was performed to evaluate the raw storage stability of the sample. The results are shown in Table 5.

[Table] Compounds listed at the top of the page (16)
As is clear from Table 5, sample No. 19 containing comparative compound (F) shows a remarkable decrease in relative sensitivity during raw storage.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing at least one compound represented by the following general formula (1). General formula (1) Y-O-D-J-PUG-B In the formula, Y represents a yellow coupler component that can cause a coupling reaction with an oxidized color developing agent to form a yellow dye, and D represents a phenylene group. In the formula, J represents a simple bond or a divalent organic group, B represents a protecting group for PUG that is bonded to PUG via a methylene group and can release PUG by a coupling reaction or a hydrolysis reaction, and PUG is -O-
DJ-PUG or PUG represents a photographically useful group.