JPH0461341B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive silver halide emulsion layer in which a blocked photographic reagent is combined which releases a photographically useful reagent. It relates to photographic materials containing. (Prior art) By adding a photographically useful photographic reagent to a photographic light-sensitive material in advance and exerting its effect, characteristics different from those obtained when the photographic reagent is contained in a processing solution can be achieved. It will be done. Its characteristics are 1)
For example, photographic reagents that easily decompose under acid/alkaline or oxidizing/reducing conditions and cannot be stored for long periods in processing baths can be used effectively, 2) Processing solution composition is simplified and preparation becomes easier, 3) Processing 4) It becomes possible to apply the necessary photographic reagents at the necessary timing, or 4) to apply the necessary photographic reagents only to the necessary locations, that is, to a certain layer of the multilayer photosensitive material and/or to the layers in its vicinity. , 5) the amount of action of the photographic reagent can be varied as a function of silver halide development, etc. However, if a photographic reagent is added to a photographic material in an active form, it may react with other components in the photographic material or decompose due to the influence of heat, oxygen, etc. during storage prior to processing. As a result, the expected performance cannot be achieved during processing. One way to solve these problems is to block the active groups of a photographic reagent and add it to the photographic material in a substantially inactive form, that is, as a photographic reagent precursor, during the development process. There is a method to generate photographic reagents for the first time. When a useful photographic reagent is, for example, a dye, blocking the functional groups that greatly affect the spectral absorption of the dye and shifting the spectral absorption toward shorter or longer wavelengths allows the dye to have the desired spectral range of sensitivity. Even if it is made to coexist in the same layer as the silver halide emulsion layer, it has the advantage that a decrease in sensitivity due to the so-called filter effect does not occur. If a useful photographic reagent is an antifoggant or a development inhibitor, by blocking the active groups, it is possible to suppress the desensitization effect due to adsorption to photosensitive silver halide during storage and the formation of silver salts, and at the same time, it is possible to By releasing these photographic reagents at the required timing during processing, there are advantages such as reducing fog without impairing sensitivity, suppressing overdevelopment fog, or stopping development at the required time. When useful photographic reagents are developing agents, co-developing agents, or nucleating agents, blocking the active or adsorbing groups can prevent various adverse photographic effects caused by the formation of semiquinones and oxidants during storage due to air oxidation. There are advantages such as prevention or prevention of electron injection into silver halide to prevent generation of fog nuclei during storage, and as a result, stable processing can be realized. Even if the photographic reagent is a bleach accelerator or a bleach/fixing accelerator,
By blocking these active groups, reactions with other components contained therein can be suppressed during storage, and by removing the protective groups during processing, the desired performance can be achieved at the required time. It has advantages. As mentioned above, the use of precursors for photographic reagents can be an extremely effective means for fully demonstrating the performance of photographic reagents.However, on the other hand, these precursors must satisfy extremely strict conflicting requirements. It has to be something. In other words, it must be able to satisfy the contradictory requirements of being stable under storage conditions, and releasing the photographic reagent promptly and efficiently by unraveling the blocking group at the required timing during processing. . Several photographic reagent blocking techniques are already known. For example, Tokuko Sho 47-44805
Those using blocking groups such as acyl groups and sulfonyl groups described in the specification of Japanese Patent Publication No. 1983-
No. 39727, No. 55-9696, and No. 55-34927, which utilize a blocking group that releases a photographic reagent through the so-called reverse Michael reaction;
39727, JP-A No. 57-135944, JP-A No. 57-135945,
A method using a blocking group that releases a photographic reagent upon the production of quinone methide or a quinone methide-like compound by intramolecular electron transfer as described in JP-A-57-136640, and a method described in JP-A-55-53330. Those that utilize intramolecular ring-closing reactions, or JP-A-57-76541, JP-A-57-135949, JP-A-57-
A technique using 5- or 6-member cleavage described in the specification of No. 179842 is known as a known technique. (Problems to be solved by the invention) However, with the conventional photographic reagent blocking technology,
For those that are stable under storage conditions, the release rate of the photographic reagent during processing is too low and requires high alkaline treatment with a pH of 12 or higher, or even if the release rate is sufficient with a processing solution of PH9-12, it cannot be stored. It has the disadvantage that it gradually decomposes under certain conditions, impairing its function as a precursor. Therefore, an object of the present invention is to provide a photographic reagent precursor which is completely stable under the storage conditions of photosensitive materials and which releases a photographic reagent at a desired timing during the development process. It is an object of the present invention to provide a photographic reagent precursor that can realize timely release of a photographic reagent even when processing with a low pH processing solution. An object of the present invention is to provide a silver halide photographic light-sensitive material containing this photographic reagent precursor. (Means for Solving the Problems) The present inventors have made various studies in order to overcome the above problems, and have found that by using a photographic reagent precursor in which a protecting group of a specific structure is bonded to a photographically useful group. , discovered that it is possible to achieve that purpose,
Based on this knowledge, we have completed the present invention. That is, the present invention provides a photographic material comprising at least one light-sensitive silver halide emulsion layer,
The present invention provides a silver halide photographic light-sensitive material containing at least one kind of photographic reagent precursor represented by the following general formula (I). (In the formula, Z represents a nonmetallic atomic group necessary to form a 5- to 7-membered ring; R ₁ , R ₂ and
R ₃ represents a hydrogen atom or a substituent; m represents an integer of 0 to 3; n represents 0 or 1; and m+n represents an integer of 1 to 3.
X represents an electrophilic bond; L represents a timing group; represents 0 to 1; PUG represents a photographically useful group. ) The present invention will be explained in more detail below. The photographically useful group represented by PUG in the above general formula (I) includes known photographic reagents bonded with a hetero atom, such as mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptobenzimidazoles,
Antifoggants and development inhibitors represented by mercaptothiadiazoles, benzotriazoles, imidazoles, etc.; developers such as p-phenylenediamines, hydroquinones, p-aminophenols; auxiliaries represented by pyrazolidones developer,
Examples include nucleating agents such as hydrazines and hydrazides; silver halide solvents such as sodium thiosulfate; bleach accelerators such as aminoalkylthiols; and azo dyes and azomethine dyes. Further, useful photographic reagents include photographic reagents that further have a redox function in which the photographic reagent is released as a function of development, such as coloring materials for color diffusion transfer sensitive materials or DIR-hydroquinones. . Furthermore, in the above general formula (I), the timing group L
is a group that is known per se and has the function of temporally shifting (timing) the availability of the residue represented by PUG. In other words, the bond between X and L is cleaved and L-PUG
L has a function such that after the residue is formed, a certain appropriate amount of time is required for the bond between PUG and L to cleave. Therefore, if L-PUG has diffusibility, it is possible to design a PUG that is generated at a location distant from the point where the precursor of the present invention is incorporated. As the timing group represented by L, for example, a photographically useful group (PUG) is released by an intramolecular ring-closing reaction of a p-nitrophenoxy derivative described in U.S. Pat. U.S. Patent No. 4310612
53330) and U.S. Patent No. 4358525, which release PUG through an intramolecular ring-closing reaction after ring cleavage; U.S. Pat.
4483919, JP-A No. 59-121328, etc., which release PUG with the formation of acid anhydride through intramolecular ring-closing reaction of the carboxyl group of succinic acid monoester or its analog; US Patent No. 4409323
No. 4421845, Research Disclosure No. 21228 (December 1981), U.S. Patent No. 4416977 (Japanese Patent Publication No. 57-135944), Japanese Patent Application Publication No. 58-209736,
No. 58-209738, etc., which generates quinomonomethane or its analogs by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group and releases PUG; US Patent No.
No. 4420554 (Unexamined Japanese Patent Publication No. 136640, No. 136640)
135945, No. 57-188035, No. 58-98728, and No. 58-209737, etc., which release PUG from the γ-position of the enamine by electron transfer of the moiety having the enamine structure of the nitrogen-containing heterocycle; 1977-
No. 56837, which releases PUG through an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with the nitrogen atom of a nitrogen-containing heterocycle; US Pat.
JP-A-59-93442, JP-A-59-75475, etc., which release PUG with the formation of aldehydes; JP-A-51-146828, JP-A-57-179842
No. 59-104641, which releases PUG by decarboxylating the carboxyl group; -O-
One that has the structure COOCR ₁ R ₂ -PUG and releases PUG with decarboxylation and subsequent production of aldehydes; releases PUG with production of isoyanate as described in JP-A-60-7429. Examples include those that release PUG through a coupling reaction with an oxidized color developer described in US Pat. No. 4,438,193 and the like. In the general formula (I), Z represents an atomic group necessary to form a 5- to 7-membered ring, and specifically includes alkylene, cycloalkylene, alkenylene, arylene, aralkylene, oxyalkylene, thioalkylene, aminoalkylene, and Examples include heterocyclene. R ₁ and R ₂ may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a sulfonyl group, a heterocyclic residue, etc. . R ₃ represents an alkyl group, an alkenyl group, a cycloalkyl group, a heterocyclic residue, an aryl group, an aralkyl group, and the like. In the general formula (I), the electrophilic bond represented by X is an electron-deficient bond center, so
It means a bond that has electrophilic reactivity toward a reaction site with high electron density, and preferable examples include carbonyl group, thiocarbonyl group, sulfonyl group, and sulfinyl group, and particularly preferable example is carbonyl group. . When the above R ₁ , R ₂ , R ₃ and Z are carbon-containing groups, the preferable range of carbon number is 1 to 18. Further, it is preferable that these groups be combined in a size that imparts immobility or semi-immobility to the entire molecule. Furthermore, these groups more preferably make the entire molecule diffusion resistant. Further, when the groups allowed for R ₁ , R ₂ , R ₃ and Z are substitutable, substitutable atoms such as carbon, nitrogen, and oxygen in the group may have a substituent. There may be a plurality of substituents, and these substituents may further have one or more substituents. Typical examples of these permissible substituents include: halogen atom, cyano group, nitro group, hydroxyl group, carboxyl group, sulfo group, G-, GO
−, GS−, GCO−, GCOO−, −CONH ₂ −, −
OCONH ₂ , −SO ₂ NH ₂ , −NHCONH ₂ −, −
NHSO ₂ NH ₂ , −SO ₂ G, −SOG, −COOG, −
NHSO ₂ G, etc., where G is an aliphatic hydrocarbon group,
Represents an aryl group or a heterocyclic group. Next, among the compounds of the present invention represented by the general formula (I), a more preferable compound is the following general formula ()
and (). In the general formula (), PUG, L, R ₁ , R ₂ ,
R ₃ , m, n have the same meaning as in general formula (I), R ₄ represents a substituent that can be substituted for benzene,
k represents an integer from 0 to 4;
In the case of , R ₄ may be different groups. In the general formula (), PUG, L, R ₁ , R ₂ ,
R ₃ , m, n have the same meaning as in general formula (I), R ₅ and R ₆ represent a hydrogen atom or a substituent, R ₅ and R ₆ together become R ₅ , and the ring carbon and double bond You may do so. Y is oxygen atom, sulfur atom,

[expression] or

Represents [formula]. R ₇ , R ₈ and R ₉ represent a hydrogen atom or a substituent; j represents 1 or 2; When j is 2, R ₈ and R ₉ on the two carbon atoms may be different, or may form a double bond or a ring between the two carbon atoms. _{Even when _ _ _ _} Rings and heterocycles may be formed. R ₄ in the general formula () is preferably a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an amino group, a hydroxy group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbonamide group , sulfonamide group, ureido group, sulfamide group, oxycarbonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, sial group, sulfo group, nitro group, etc. R ₅ and R ₆ in the general formula () may be the same or different, and preferably represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an exo double bond. R ₇ preferably represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a heterocyclic residue, an aryl group, an aralkyl group, and the like. R ₈ and R ₉ preferably represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. Particularly preferably in general formulas () and (), R ₁ and R ₂ represent a hydrogen atom, m represents 1 or 2, and when m is 1, n represents 1, and m
When is 2, n represents 0. In the general formula (), Y is particularly preferably
sulfur atom, or

[Formula], j represents 1, and R ₅ and R ₆ are particularly preferably a hydrogen atom, an alkyl group, and R ₅ when X is a sulfur atom.
represents the exo double bond formed by R ₆ and
but

In the case of [Formula], hydrogen atom, halogen atom child, alkyl group or

It shall form an unsaturated ring with the carbon atom of [Formula]. The reason why the precursor compound of the present invention has excellent storage stability and releases photographically useful groups quickly during processing is not clear, but it can be considered as follows. First, it is presumed that the mechanism of release of photographically useful groups from the precursor compound of the present invention is initiated by the nucleophilic reagent Nu, as shown in Scheme 1. The case where X is a carbonyl group in general formula (I) is shown. The same can be considered when X is another group. In scheme 1, PUG, L, Z, R ₁ ,
R ₂ , R ₃ , m, n and have the same meanings as in general formula (I), and Nu represents a nucleophile. In Scheme 1, the formation of () by ring cleavage of (I) does not occur at all in water due to the specific properties of the thiocarbonyl group in (I), and does not occur in water at all due to the ring cleavage of (I). , sulfite ions, amines, hydroxylamines, and hydroxyl ions).
Since the generated () has a mercapto anion with very high nucleophilicity, it immediately attacks the intramolecular electrophilic bond X to generate (V), and then cleaves the bond to generate (). . In addition,()
The intramolecular nucleophilic reaction of (V) from (V) is affected by the size of the ring produced, but it is
The case where +n=1 to 3 is preferable because the reaction rate is large. Therefore, the precursor compound of the present invention is (I)
→The reaction of () hardly occurs in the film membrane during storage and it is stable, but during processing, it becomes () due to the reaction with the nucleophile, and ()→(V)→()+
It is thought that because the reaction () occurs quickly, it is possible to achieve both stability during storage and timely release of the photographic reagent during processing. In the present invention, the preferred amount of the photographic reagent precursor added varies depending on the type of photographic reagent released from the photographic reagent precursor, but the antifoggant and development inhibitor are preferably added in an amount of 10 ^-8 to ^{10 -1} mol per mol of silver. Mercapto antifoggant is 10 ^-6
~10 ^-1 mol, an azole antifoggant such as benzotriazole from 10 ^-5 to ^{10 -1} mol, a developer from 10 ^-2 to 10 mol per mol of silver, preferably 0.1 to 5 mol,
Pyrazolidone auxiliary developer is 10 ^-4 per mole of silver.
~10 mol, preferably from 10 ^-2 to 5 mol, and the nucleating agent is 10 -2 to 10 ^-6 mol, preferably from 10 ^-3 to 10 ^-6 mol per mole of silver.
10 ^-5 mol, silver halide solvents such as hypo, 10 ^-3 to 10 mol, preferably 10 ^-2 to 1 mol, bleaching accelerators such as aminoethanethiols, 10 ^-5 per mol of silver. ~0.1 mol, preferably 10 ^-4 ~
10 ^-2 mol, dyes or color diffusion transfer photographic colorants from 10 ^-3 to 1 mol per mol of silver, preferably 5
×10 ⁻³ to 0.5 mol. Next, specific examples of precursors used in the present invention will be shown, but the invention is not limited thereto. The precursor compound used in the present invention is synthesized, for example, by the synthesis method shown in Scheme 2 below. (In Scheme 2, PUG,L,,R ₁ ,
R ₂ , R ₃ , X, m, n and Z have the same meanings as in general formula (I), and L' represents a leaving group. ) That is, dehydration condensation of () and (); ()
Ring-closing reaction using the addition reaction product of and carbon disulfide as a nucleophile; or
) with nucleophile (XI); or ()
Intermediate (X) is obtained by monothiocarbonylation with P ₄ SO ₁₀ , etc., and after converting this to active halide (XV), it is reacted with PUG-(L) anion, or (X) is converted to active halide (XV). A compound represented by general formula (I) can be obtained by reacting with (X) having the following. A specific synthesis example will be described below. Synthesis Example 1 Synthesis of Exemplified Compound (1) Carbon disulfide (7.2 g,
0.095 mol) was added dropwise, and stirring was continued for about 5 hours to produce β-alanine dithiocarbamic acid triethylamine salt. α-Ethyl chloroacetate (12.3 g, 0.1 mol) was added dropwise to the reaction solution, and the mixture was heated at 5°C for 30
After stirring for 3 hours at about 50°C, the solvent was distilled off under reduced pressure. N-(3-carboxyethyl)rhodanine was removed by washing the residue with cold water.
I got 16g. The obtained rhodanine derivative (10.2g,
0.05 mol) of N,N-dimethylacetamide (40
ml) solution under ice cooling with t-butoxypotassium (6.2 g,
After stirring for 30 minutes, 1-phenyl-
A solution of 4-bromomethyl-tetraziline-5-thione (13.5 g, 0.05 mol) in N,N-dimethylacetamide (50 ml) was added dropwise. After the dropwise addition was completed, the reaction solution was stirred at room temperature for about 2 hours and poured into ice water. A crude oil was obtained by extraction with ethyl acetate, drying with Glauber's salt, and evaporation of the solvent. Separation and purification by silica gel column chromatography yielded 7.3 g of Exemplary Compound (1). The structure is determined by mass spectra and
Confirmed by NMR spectrum. Synthesis Example 2 Synthesis of Exemplified Compound (8) P ₂ S ₅ (5 g, 0.023 mol) was added to a solution of phthalimide (14.7 g, 0.1 mol) in benzene (150 ml) under ice cooling, and then heated under reflux for 1 hour. After washing the penzene layer with water and then with 2N-HC, the benzene was distilled off under reduced pressure. Acetic acid (50 ml) and 30% formalin (20 ml) were added to the resulting reaction product, and stirring was continued at room temperature for 5 hours. . Add water to the reaction solution and filter the precipitated crystals to obtain N-hydroxymethylmonothiophthalimide.
Obtained 11.3g. To a solution of the obtained monothiophthalimide compound (9.6 g, 0.05 mol) in benzene (100 ml) was added phosphorus tribromide (13.4 g, 0.05 mol), and the mixture was heated under reflux for 1 hour. The benzene layer was separated and benzene was distilled off under reduced pressure to obtain 11.2 g of crude crystals of the bromomethyl compound. The above bromomethyl compound (7.6 g, 0.03 mol) was gradually added to a solution of n-propylamine (4.1 g, 0.07 mol) in tetrahydrofuran (50 ml) at about 5°C. The reaction solution was stirred at room temperature for 1 hour, poured into ice water, extracted with ethyl acetate, dried with sodium sulfate, and the solvent was distilled off to obtain a crude oil of the corresponding propylaminomethyl compound. This product was added to a mixed solution of N,N-dimethylacetamide (50 ml) and triethylamine (3.3 g, 0.033 mol) without purification.
A solution of (3-methylureidophenyl)-5-tetrazolylthio]carbonyl (16 g, 0.03 mol) in tetrahydrofuran (50 ml) was added dropwise. Subsequently, stirring was continued at room temperature for about 3 hours, and the reaction solution was poured into ice water. Extraction with ethyl acetate, drying with Glauber's salt, and evaporation of the solvent gave a crude oil. Exemplary compounds were separated and purified by silica gel column chromatography.
7.5g of (8) was obtained. The structure is determined by mass spectra and
Confirmed by NMR spectrum. The precursor compounds of the present invention may be used in combination of two or more. The blocked photographic reagent (precursor) of the present invention can be used in silver halide emulsion layers, colorant layers, undercoat layers, protective layers, intermediate layers, etc. of silver halide photographic light-sensitive materials.
Filter layer, anti-halation layer, image receiving layer,
It may be added to any of the cover sheet layer and other auxiliary layers. In order to add the precursor used in the present invention to these layers, the precursor can be added to the coating solution for layer formation either as is or in a solvent that does not have an adverse effect on the photographic material, such as water or alcohol. It can be added after being dissolved at an appropriate concentration. Alternatively, the precursor can be added by dissolving the precursor in a high boiling point organic solvent and/or a low boiling point solvent and emulsifying and dispersing it in an aqueous solution. Also, JP-A No. 51-39853, No. 51-59942, No. 54-
32552, US Pat. No. 4,199,363, etc., it may be impregnated into a polymer latex and added. Although the precursor of the present invention may be added at any time during the manufacturing process, it is generally preferable to add it immediately before coating. The compounds of the present invention can be used, for example, in coupler type color photographic materials. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image forming agents, which are complementary colors, respectively. is used. Normally, color photographic materials are roughly divided into two types: an external method in which couplers are placed in a developing solution, and an internal method in which couplers are incorporated in each photosensitive layer of the material so as to maintain independent functions. Ru. In the latter, the dye image-forming coupler is added to the silver halide emulsion. Couplers added to the emulsion must be non-diffusible (diffusion resistant) in the emulsion binder matrix. In the internal mold method, the processing process for color photographic materials basically consists of the following three steps. (1) Color development step (2) Bleaching step (3) Fixing step The bleaching step and the fixing step can be performed simultaneously. That is, the bleach-fixing process (so-called Blix)
Through this step, developed silver and undeveloped silver halide are desilvered. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process involves the following steps in order to maintain the photographic and physical quality of the image.
Alternatively, an auxiliary process is involved, such as to improve the storage stability of the image. For example, a hardening bath is used to prevent excessive softening of the photosensitive film during processing, a stop bath is used to effectively stop the development reaction, an image stabilization bath is used to stabilize the image, and a removal bath is used to remove the backing layer of the support. Examples include processes such as a membrane bath. Conventionally known methods of adding or dispersing couplers to emulsions and methods of adding them to gelatin/silver halide emulsions or hydrophilic colloids are applicable. For example, a method of mixing and dispersing a coupler with a high boiling point organic solvent such as dibutyl phthalate, tricresyl phosphate, wax, higher fatty acids and their esters, etc., for example, US Pat.
2322027, etc. Another method is to mix and disperse the coupler with a low boiling point organic solvent or a water-soluble organic solvent. A method of dispersing couplers in combination with a high boiling point organic solvent. For example, US Patent No.
2801170, 2801171, 2949360, etc., when the coupler itself has a sufficiently low melting point (for example, 75°C or less), it may be used alone or in combination with other couplers, such as colored couplers. Dispersion method using in combination with an uncolored coupler, etc. For example, the description in German Patent No. 1143707 is applicable. Dispersion aids include commonly used anionic surfactants (e.g., sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate, Fischer-type couplers, etc.), and amphoteric interfaces. Active agents (for example, N-tetradecyl/N.N dipolyethylene α betaine, etc.) and nonionic surfactants (for example, sorbitan, monolaurate, etc.) are used. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color-forming coupler, which is formed by oxidative coupling with an aromatic primary amine developer (e.g., phenylenediamine derivative, aminophenol derivative, etc.) in the color development process. It may also contain a compound that can develop color. For example, as a magenta coupler,
There are 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc.
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product may contain a colorless DIR coupling compound that is colorless and releases a development inhibitor. When the photographic element of the present invention is applied to color diffusion transfer photography, peel-apart type or
50-13040 and British Patent No. 1330524, or a peel-free type film unit as described in JP-A-57-119345. can. The compounds of the present invention can also be used in black-and-white photographic materials. Examples of black-and-white photosensitive materials include X-ray film for direct medical use, black-and-white film for general photography, lithographic film, and scanner film. Other constitutions of the silver halide photographic material of the present invention, such as a method for producing a silver halide emulsion, halogen composition, crystal habit, grain size, chemical sensitizer, antifoggant, stabilizer, surfactant, gelatin There are no particular restrictions on hardening agents, hydrophilic colloid binders, matting agents, dyes, sensitizing dyes, anti-fading agents, anti-color mixing agents, polymer latexes, brighteners, antistatic agents, etc. (Research Disclosure) Volume 176 No. 22
You can refer to the description on pages 31 to 31 (December 1978). The compound of the present invention is also suitable for activator treatment in which a color developing agent or its precursor is incorporated into a light-sensitive material and treated in an alkaline bath. Furthermore, when the activator treatment is performed at a high temperature of 50° C. or higher, it is possible to select a precursor that is advantageous in terms of storage stability, and the compounds of the present invention can also be used for such purposes. Furthermore, there are no particular limitations on the exposure method, development method, etc. of the silver halide photographic material of the present invention.
For example, Research Disclosure No. 28~
Any of the known methods and known treatment liquids as described on page 30 can be applied.
This photographic processing may be either a photographic processing for forming a silver image (black and white photographic processing) or a photographic processing for forming an increased dye (color photographic processing), depending on the purpose. The processing temperature is usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used. In particular, when processing at a high temperature of 50° C. or higher, the release rate of photographically useful reagents from the precursor increases, making it possible to select a precursor that is advantageous in terms of storage stability. The developer used in black-and-white photographic processing can contain known developing agents. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. may be used alone or in combination. I can do it. The developing solution generally contains other well-known preservatives, alkaline agents, PH buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toning agents, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like. The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" processing is used for photographic reproduction of line images or halftone dots.
Usually, dihydroxybenzenes are used as the developing agent, and the development process is carried out contagiously under low sulfite ion concentration. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known general aromatic amine developer, such as phenylene diamines (e.g., 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-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. In addition, “Photo Processing Chemistry” by LFA Mason (published by Focal Press) [LFMason
Photographic Processing Chemistry (Focal
Press], 1966), pp. 226-229, U.S. Patent
Those described in No. 2193015, No. 2592364, JP-A-48-64933, etc. may be used. (Effects of the Invention) The silver halide photographic light-sensitive material of the present invention has the excellent effect of being stable under storage conditions and releasing photographic reagents promptly and efficiently at the required timing during processing. . In particular, the silver halide photographic light-sensitive material of the present invention achieves timely release of photographic reagents even when processed with a processing solution having a relatively low pH of 9 to 12. Further, the present invention has excellent effects in that desensitization due to the addition of a photographic reagent precursor can be prevented and the function of the released photographic reagent can be exerted. Example 1 In order to evaluate the effectiveness of antifoggant precursors in the present invention, compounds of the present invention and their control compounds, a first compound was prepared on a cellulose triacetate film support provided with a subbing layer. The antifoggants shown in the table and the blocked antifoggants of the present invention were combined with a coupler (Cp-
1) Dissolved in tricresyl phosphate with
By applying an emulsion layer that has been emulsified and added,
Samples A to E were prepared. The amount of each substance applied is g/m ²
Or shown in the box as mo/m ² . (1) Emulsion layer Negative silver iodobromide emulsion, grain size 1.4μ
(Silver 1.6×10 ^-2 mo/m ² ) Magenta coupler Cp-1
(1.3×10 ^-3 mo/m ² ) Antifoggant or its precursor
(Specified in Table 1) Gelatin (2.50g/m ² ) (2) Protective layer Gelatin (1.30g/m ² ) 2,4-dichloro-6-hydroxy-s-triazine sodium salt (0.05g/m ² ) This photographic element was exposed to 25 CMS using a tungsten light source with a color temperature adjusted to 4800°K using a filter, and then developed at 38°C according to the processing steps described below. Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the processing solution used in each step was as follows. Color developer Diethylenetriaminepentaacetic acid 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4-(N- Ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5g Add water 1.0 PH10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt
100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water to 1.0 PH6.0 Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium sulfite 4.6g Add water 1.0 PH6.6 Stabilizer Formalin (40%) 2.0ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization≒10) 0.3g Add water 1.0

[Table] Values for cases.
From Table 1, it can be seen that in B to C using the compounds of the present invention, fog was reduced with almost no decrease in sensitivity. On the other hand, when the precursor compound and antifoggant described in JP-A No. 57-135949 are directly added, the sensitivity decreases significantly. Therefore, the precursor compound of the present invention exists stably in the film, and It can be said that by releasing the anti-fogging agent at the right time, fog can be specifically reduced without desensitizing. The comparative antifoggants and couplers used here are as follows. Example 2 To evaluate the effectiveness of the (co-developer) precursor in the present invention, compounds of the present invention and their control compounds were coated on a cellulose triacetate film support provided with a subbing layer. Samples G~ K was prepared. The application amount of each substance is g/ ^m2 or mo
/m ² shown inside the cutlet. (1) Emulsion layer Negative silver iodobromide emulsion, grain size 1.4μ
(Silver 1.6×10 ^-2 mo/m ² ) Magenta coupler Cp-1
(1.33×10 ^-3 mo/m ² ) (auxiliary developer) or its precursor
(1.33×10 ^-3 mo/m ² ) Gelatin (2.50g/m ² ) (2) Protective layer Gelatin (1.30g/m ² ) 2,4-dichloro-6-hydroxy-s-triazine sodium salt (0.05g /m ² ) After these films were left for 14 hours at 40° C. and 70% relative humidity, they were subjected to imagewise exposure for sensitometry, and color development was performed in the same manner as in Example 1. The photographic properties obtained are shown in Table 2.

[Table] As is clear from the results in Table 2, Samples H and I using the compounds of the present invention are sensitized with almost no increase in fog. On the other hand, JP-A-55
Auxiliary developer precursor (2) described in No.-53330
-A) Sample J uses almost no increase in sensitivity. Further, in sample K to which the auxiliary developer (2-B) was added as is, fog increased and desensitization occurred. Comparative compounds 2-A and 2-B used here are as follows.

Claims (1)

[Scope of Claims] 1. A photographic light-sensitive material comprising at least one light-sensitive silver halide emulsion layer, characterized in that it contains at least one kind of photographic reagent precursor represented by the following general formula (I). Silver halide photographic material. (In the formula, Z represents a nonmetallic atomic group necessary to form a 5- to 7-membered ring; R ₁ , R ₂ and
R ₃ represents a hydrogen atom or a substituent; m represents an integer of 0 to 3; n represents 0 or 1; and m+n represents an integer of 1 to 3.
X represents an electrophilic bond; L represents a timing group; represents 0 or 1; PUG represents a photographically useful group. )