JPH0762757B2 - Silver halide photographic light-sensitive material - Google Patents

Description

The present invention relates to a photographic light-sensitive material in which a photosensitive silver halide emulsion layer and a photographic reagent precursor which releases a photographically useful reagent in a timely manner during photographic processing are combined.

(Prior Art) By adding a photographically useful photographic reagent to a photographic light-sensitive material in advance and exerting its effect, a characteristic different from that obtained when a photographic reagent is contained in a processing solution is achieved. To be Its features are: 1) It can be easily decomposed under acid / alkali or oxidation / reduction conditions and can effectively use photographic reagents that do not withstand long-term storage in a processing bath. 2) Simplifies the composition of the processing solution and facilitates preparation. 3) It is possible to activate the required photographic reagent at the required timing during processing. 4) The photograph required only at the required place, that is, in a specific layer having a multilayer photosensitive material and / or a layer in the vicinity thereof. And 5) the working amount of the photographic reagent can be changed as a function of silver halide development. However, if the photographic reagent is added to the photographic light-sensitive material in an active form, it may react with other components in the photographic light-sensitive material during storage before processing or decompose under the influence of heat or oxygen. As a result, the expected performance cannot be achieved during processing.

As one method of solving such a problem, the active groups of the photographic reagent are blocked, and the photographic reagent is added in the form substantially inactive in the photographic material, that is, as a photographic reagent precursor in the photographic material, and is added at the time of development processing. There is a method to generate a photographic reagent for the first time.

According to this method, when a useful photographic reagent is a dye, for example, by blocking a functional group that greatly affects the spectral absorption of the dye and shifting the spectral absorption to the short wavelength side or the long wavelength side, the desired Even if they are made to coexist in the same layer as the silver halide emulsion layer having a light-sensitive spectrum region, there is an advantage that the sensitivity is not lowered by the so-called filter effect. Further, if the useful photographic reagent is an antifoggant or a development inhibitor, blocking the active group can suppress the desensitization effect due to the adsorption to the photosensitive silver halide during storage and the formation of a silver salt. By releasing these photographic reagents at the necessary timing during development processing,
There are advantages that fog can be reduced without deteriorating sensitivity, overdevelopment fog can be suppressed, or development can be stopped at a necessary time. When useful photographic reagents are developing agents, auxiliary developing agents, development accelerators, or nucleating agents, blocking active groups or adsorbing groups can cause various photographic effects due to the formation of semiquinones or oxidants by air oxidation during storage. There is an advantage in that the generation of fog nuclei during storage is prevented by preventing adverse effects or by injecting electrons into silver halide, and as a result, stable processing can be realized. Even when the photographic reagent is a bleaching accelerator or a bleaching / fixing accelerator, by blocking their active groups, the reaction with other components contained therein can be suppressed during storage and the protective groups can be removed during processing. The advantage is that the desired performance can be exhibited at the required time.

As described above, the use of photographic reagent precursors can be an extremely effective means for sufficiently exhibiting the performance of photographic reagents, however, on the other hand, those precursors satisfy extremely severe conflicting requirements. Must be one. That is, it must be stable under storage conditions, and be able to satisfy the contradictory requirements that during processing, the blocking group is released at the required timing and the photographic reagent is released promptly and efficiently. .

Several techniques are already known as a block technology for photographic reagents. For example, those utilizing a blocking group such as an acyl group and a sulfonyl group described in JP-B-47-44805, JP-B-54-39727, JP-B-55-9696, and JP-B-55-9696.
-34927 utilizing a blocking group which releases a photographic reagent by a so-called reverse Michael reaction, JP-B-54-39727, JP-A-57-135944, 57-135945.
No. 57-136640, utilizing a blocking group that releases a photographic reagent with the formation of a quinone methide or a quinone methide-like compound by intramolecular electron transfer.
Those utilizing the intramolecular ring closure reaction described in JP-A-55-53330, or JP-A-57-76541 and 57-135.
Known techniques include those utilizing 5-membered or 6-membered cleavage described in Japanese Patent Nos. 949 and 57-179842.

(Problems to be solved by the invention) However, in the conventional photographic reagent blocking technology, when a photographic reagent that is stable under storage conditions is processed, the release rate of the photographic reagent is too small and a high alkaline treatment of pH 12 or higher is required. However, in the case of heat development, a very high temperature was required or a long heat development time was required. In addition, it has the drawback that it decomposes gradually under storage conditions even if the release rate is sufficient with a processing solution having a pH of 9 to 12 or a normal heat development process, and that it also impairs its function as a precursor.

When using the above high pH developer (pH 12 or more), the developer is easily oxidized by air, and the storage stability of the developer decreases,
It is difficult to handle because it promotes corrosion of the developing bath and the skin becomes more irritating. Further, maintaining the photographic sensitivity and the stability of the generated image is not so easy as with a high pH developer.

Therefore, an object of the present invention is to provide a photographic reagent precursor which is completely stable under the storage conditions of a light-sensitive material and releases a photographic reagent at a desired timing during development processing, and particularly at a relatively low pH of 9 to 12. Another object of the present invention is to provide a photographic reagent precursor capable of realizing a timely release of a photographic reagent even in the case of performing the processing solution of 1. The object of the present invention is to provide a silver halide photographic light-sensitive material containing this photographic reagent precursor.

(Means for Solving Problems) As a result of various studies to overcome the above problems, the inventors have used a photographic reagent precursor in which a protecting group having a specific structure is bonded to a photographically useful group. As a result, they have found that the object can be achieved, and have completed the present invention based on this finding.

That is, the present invention provides a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one photographic reagent precursor represented by the following general formula [I].
The present invention provides a silver halide photographic light-sensitive material characterized by containing a seed.

General formula [I] (Wherein R ₁ represents a hydrogen atom or a substituent; Y represents an oxygen atom or = NR ₂ (R ₂ represents a substituent); T represents a timing group; L represents a linking group; X Represents an electrophilic center; PUG forms an oxygen atom, a sulfur atom or a ring,
And a photographically useful group in which at least one of the adjacent atoms is a nitrogen atom, which is a nitrogen atom; m represents 0 or 1, and n represents 0 or 1. When m is 1, Y and X are bonded to each other via 3 to 5 atoms. ) The group represented by R ₁ is preferably an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic residue, and these groups may have a substituent.

Preferably as a substituent, 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 carbonamido group, a sulfonamide group, Examples thereof include ureido group, sulfamide group, oxycarbonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, cyano group, sulfo group and nitro group.

Y represents an oxygen atom or ═NR ₂ , and R ₂ preferably represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic residue.

L preferably represents an alkylene group, a cycloalkylene group, an arylene group, an aralkylene group, an alkyleneamino group, an aryleneamino group or a heterocyclene group.

X preferably represents a carbonyl group, a sulfonyl group, a sulfinyl group, or a thiocarbonyl group, and X and Y are preferably bonded via 3 to 5 atoms.

Examples of the timing group represented by T include p-type groups described in U.S. Pat. No. 4,248,962 (JP-A-54-145135) and the like.
Releasing a photographically useful group (said PUG) by an intramolecular ring closure reaction of a nitrophenoxy derivative; US Pat. No. 4,31
Nos. 0,612 (JP-A-55-53330) and 4,358,525 which release PUG by an intramolecular ring closure reaction after ring cleavage; U.S. Pat. Nos. 4,330,617 and 4,446,216;
U.S. Pat. No. 4,409,323, which discloses the production of an acid anhydride by the intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or its analogs described in JP-A No. 4,483,919 and JP-A-59-121328; No. 4,421,845, Research Disclosure No. 21228 (December 1981),
Electrons via a double bond conjugated with an aryloxy group or a heterocyclic oxy group described in U.S. Pat. No. 4,416,977 (JP-A-57-135944), JP-A-58-209736, JP-A-58-209738, etc. Release of PUG by forming quinomonomethane or its analog by transfer; US Pat. Nos. 4,420,554 (JP-A-57-136640), JP-A-57-135945 and 57-
188035, 58-98728 and 58-209737, which release PUG from the γ-position of the enamine by electron transfer of the portion having the enamine structure of the nitrogen-containing heterocycle described in JP-A-57-56837. Releasing a PUG by an intramolecular ring-closing reaction of an oxy group produced by electron transfer to a carbonyl group conjugated with a nitrogen atom of a nitrogen-containing heterocycle described in U.S. Pat. No. 4,146,396 (JP-A-52-90932), JP 59-93
No. 442 and Japanese Patent Application No. 59-75475, which release PUG with the formation of aldehydes; JP-A-51-146828,
Nos. 57-179842 and 59-104641 which release PUG with decarboxylation of the carboxyl group; -O-COOCR ₁₁
R ₁₂ -PUG (R ₁₁ and R ₁₂ represent a substituent) structure, and releases PUG with decarboxylation and subsequent formation of aldehydes; described in Japanese Patent Application No. 59-106224. From the α-position of the nitrogen atom, forming an imino bond by electron transfer of the nitrogen atom
Those releasing PUG; those generating PUG with the formation of aldehydes and imines described in Japanese Patent Application No. 59-106223; PUG with formation of isoianaates described in JP-A-60-7429 Releasing PUG by a coupling reaction with the oxidant of the color developing agent described in US Pat. No. 4,438,193; oxidized by the oxidant developing agent described in Japanese Patent Application No. 59-33059 Examples include those that release PUG by post-nucleophilic attack and subsequent withdrawal reaction.

The photographically useful group represented by PUG is released during photographic processing and serves as a photographic reagent. Therefore, a photographically useful group is a known photographic reagent bonded at a hetero atom, for example, mercaptotetrazole, mercaptotriazole, mercaptopyrimidine, mercaptobenzimidazole, mercaptothiazoazole, benzotriazole, imidazole. Antifoggants and development inhibitors represented by, for example; developing agents such as hydroquinones and p-aminophenols; auxiliary developing agents represented by pyrazolidones, development accelerators such as hydrazines and hydrazides, or nucleating agents. A silver halide solvent such as sodium thiosulfate;
Bleaching accelerators such as aminoalkyl thiols; or azo dyes, azomethine dyes and the like. Further, as a function of development, a photographic reagent further having a redox function for releasing the photographic reagent, for example, a color material for a color diffusion transfer photosensitive material or RIR-hydroquinones can be mentioned as a useful photographic reagent. .

R ₁ more preferably represents a cycloalkyl group, an aryl group or a heterocyclic residue, particularly preferably a phenyl group or a naphthyl group.

The substituent for R ₁ is more preferably an alkyl group (eg, methyl group, t-butyl group, pentadecyl group, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), alkoxy group (eg, methoxy group, octyloxy group, hexa). Decyloxy group etc.), amino group (eg dimethylamino group, dioctylamino group, N-methylhexadecylamino group etc.), hydroxy group, acyl group (eg propanoyl group, decanoyl group, benzoyl group etc.), sulfonyl group (eg Octyl sulfonyl group, benzene sulfonyl group, etc.), carbonamino group (eg, N-methylamitoamide group, N-decylbutyramide group, etc.), sulfonamide group (eg, N-methylmethanesulfonamide group, N-phenylethanesulfonamide) Group), carbonyloxy group ( For example, it represents a propionyloxy group, an octanoyloxy group, a hexadecanoyloxy group, a benzoyloxy group, etc.), a cyano group, a nitro group, a heterocyclic residue (eg morpholino, 1-pyrazolyl, 4-pyridyl etc.), and particularly preferably Represents an alkyl group, a halogen atom, an alkoxy group, an amino group, a fodoxy group, a cyano group or a nitro group.

Y particularly preferably represents an oxygen atom.

L more preferably represents an alkylene group, an arylene group, an alkyleneamino group or an aryleneamino group,
Particularly preferably, it represents an alkylene group or an arylene group.

X more preferably represents a carbonyl group or a sulfonyl group, and particularly preferably a carbonyl group.

X and Y are more preferably bonded between them via 3 to 4 atoms, particularly preferably via 3 atoms.

T more preferably represents a timing group that releases PUG by electron transfer, and particularly preferably a timing group that forms formalin, carbon dioxide, or formalin and carbon dioxide at the same time to release PUG.

The photographically useful group represented by PUG more preferably represents an antifoggant, an auxiliary developing agent, a hydroquinone, or a paint, and particularly preferably an antifoggant or an auxiliary developing agent.

As precursors having a structure similar to the present invention, amine precursors disclosed in JP-A-59-157637 and precursors of carboxylic acids disclosed in JP-A-60-108837 are known. Each of these releases these amines or carboxylic acids by a deprotection reaction under thermal development conditions. The precursor of the present invention is characterized in that the photographically useful group is an oxygen atom, a sulfur atom or a ring and a nitrogen atom in which any one of the adjacent atoms is a nitrogen atom is bonded, and therefore, the photograph from the precursor We have succeeded in remarkably increasing the ability of leaving useful groups. Therefore, the precursor of the present invention does not require a high temperature treatment of 80 ° C. or higher as described in the above-mentioned Japanese Patent Publication for deprotection, and can release a photographically useful group at a processing temperature of 80 ° C. or lower. .

Specific examples of the compound of the present invention are shown below, but the invention is not limited thereto.

The compounds of the present invention can be prepared by
By the reaction of oximes [II] with active halides [III]
Can be easily synthesized. Aldoximes [I
I] is, for example, Organic Syntheses Vol. 2, pp. 313, 19
43 years (Organic Synthesis, Vol.2, 31 (1943); JP Sho 60
It is synthesized by the method described in JP-A-108837. Active Harai
[III] is a compound of the corresponding carboxylic acid thionyl chloride.
Or a halogenating agent (when m = 1)
With gen or dihaloketoimines T_nReaction with PUG
Is synthesized by. The reaction between [II] and [III] is
Nitrile, ether, tetrahydrofuran, N, N-dimethyl
Solubility of tylformamide, N, N-dimethylacetamide, etc.
In a medium, an organic base (for example, pyridine, 4-dimethylamino
Pyridine, triethylamine, etc.), sodium hydroxide,
Can be performed in the presence of sodium methylate, etc.
It

(In Scheme 1, PUG, T, L, X, Y, R ₁ ,
m and n have the same meanings as in formula [I], and Z represents a halogen atom.

A specific synthesis example is shown below.

Synthesis Example 1 Synthesis of Exemplified Compound (1) Sodium salt of 2-methoxy-1-naphthaldoxime (4.46) synthesized by the method described in JP-A-60-108837.
g, 0.02 mol) in tetrahydrofuran (50 ml), a solution of pis (1-phenyl-5-tetrazolylthio) carbonyl (7.6 g, 0.02 mol) in tetrahydrofuran (40 ml) was added dropwise at about 5 ° C. Approximately 1 at that temperature after dropping
Stir for hours. The reaction solution was poured into ice water, and the precipitated crystals were collected by filtration to obtain 7.2 g of Exemplified compound (1). mp112-115 ° C. The structure was confirmed by mass spectrum and NMR spectrum.

Synthesis Example 2 Synthesis of Exemplified Compound (7) Phthalic anhydride (4.5 g, 0.03 mol) and 1,5-diphenylpyrazolidin-3-one (7.1 g, 0.03 mol) in methylene chloride (about 5 ° C. in 100 ml solution). At triethylamine (3.3g,
0.033 mol) was added dropwise, followed by stirring at room temperature for 2 hours.
The reaction solution was cooled to about 5 ° C, 2N-HCl was added, and the precipitated crystals were collected by filtration to give crude crystals of 2- (1,5-diphenyl-3-pyrazolinyloxycarbonyl) benzoic acid. The obtained crude crystals were added to acetonitrile (100 ml), thionyl chloride (6 g, 0.06 mol) was further added, and the mixture was heated under reflux for 1 hr. The solvent was distilled off under reduced pressure, and the corresponding acid chloride compound was about 11 g.
Got Subsequently, the obtained acid chloride form was dissolved in tetrahydrofuran (70 ml), and this solution was heated at about 5 ° C. to give sodium salt of 4-dodecyloxybenzaldoxime (9.
15 g, 0.03 mol) was added dropwise to a tetrahydrofuran (100 ml) solution. After the completion of dropping, the mixture was stirred at room temperature for about 1 hour. The reaction liquid was poured into ice water, and the precipitated crystals were collected by filtration to obtain 13.2 g of Exemplified compound (7). mp108-110 ° C. The structure was confirmed by mass spectrum and NMR spectrum.

The precursor of the present invention releases PUG by the mechanism shown in Scheme 2 (when X is a carbonyl group) when m is 1 and by the mechanism shown in Scheme 3 when m is 0. It is presumed to be present, but details are unknown.

(However, in Schemes 1 and 2, PUG, T, n,
L, Y, and R ₁ have the same meaning as in formula [I]. In the present invention, the preferable addition amount of the photographic reagent precursor depends on the type of photographic reagent released from the photographic reagent precursor, but the antifoggant and the development inhibitor are silver 1
Per mol, 10 ^-8 to 10 ^-1 mol, preferably a mercapto antifoggant 10 ^-6 to 10 ^-1 mol, an azole antifoggant such as benzotriazole 10 ^-5 to 10 ^-1 mol, a developer Is 10 ^-2 to 10 mol, preferably 0.1 to 5 mol, per mol of silver, and the pyrazolidone-based auxiliary developing agent is 10 ^-4 to 1 mol per mol of silver.
10 mol, preferably 10 ^{-2 to} 5 mol, the nucleating agent is 10 ^-2 to 10 ^-6 mol, preferably 10 ^-3 to 10 ^-5 mol, and the bleaching accelerator such as aminoethanethiol is 1 mol of silver. 10 per mole of silver
^{-5 to} 0.1 mol, preferably 10 ^-4 to 10 ^-2 mol, and dye or color diffusion transfer photographic colorant is 10 ^-3 to 1 per mol of silver.
The molar amount is preferably 5 × 10 ^{−3 to} 0.5 mol.

The precursors for the photographic reagents used in the present invention may be used in combination of two or more kinds.

The blocked photographic reagent (precursor) of the present invention is
Silver halide emulsion layer, color material layer, undercoat layer, protective layer, intermediate layer, filter layer, antihalation layer, image receiving layer or cover sheet layer of black and white or color diffusion transfer method of silver halide photographic light-sensitive material, and other auxiliary It may be added to any of the layers.

To add the precursor used in the present invention to these layers, in the coating solution for forming the layer, the precursor is used as it is, or in a solvent that does not adversely affect the photographic material, such as water or alcohol. It can be added after being dissolved in an appropriate concentration. Further, the precursor may be dissolved in a high boiling point organic solvent and / or a low boiling point solvent and then emulsified and dispersed in an aqueous solution and added. Further, the polymer latex may be impregnated and added by the method described in JP-A Nos. 51-39853, 51-59942, 54-32552, and U.S. Pat. No. 4,199,363.

The precursor of the present invention may be added at any time during the production process, but it is generally preferable to add it immediately before coating.

The compound of the present invention can be used, for example, in a coupler type color photographic light-sensitive material.

As a general method for forming a color image from a color photographic light-sensitive material, a subtractive color method is used, and yellow, magenta, and cyan, which have a complementary color relationship with silver halide emulsions selectively sensitive to blue, green, and red, respectively. Color image forming agents are used. For example, acylacetanilide or dibenzoylmethane type couplers are used for forming yellow color images, and pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indazolone type couplers are mainly used for forming magenta color images. , Phenolic couplers such as phenols and naphthols are mainly used to form cyan images.

Generally, color photographic light-sensitive materials are roughly classified into an external type in which a coupler is put in a developing solution and an internal type in which a coupler is contained in each photosensitive layer of the photosensitive material so as to maintain an independent function. It In the latter, dye image-forming couplers are incorporated in the silver halide emulsion. The coupler added to the emulsion must be non-diffused (diffused resistant) in the emulsion binder matrix.

In the internal method, the process of processing a color photographic light-sensitive material basically consists of the following three processes.

(1) Color development step (2) Bleach step (3) Fixing step The bleaching step and the fixing step can be performed simultaneously. That is, it is a bleach-fixing step (so-called brix), in which developed silver and undeveloped silver halide are desilvered. In addition to the two basic steps of color development and desilvering described above, the actual development process includes auxiliary steps such as maintaining the photographic and physical quality of the image or improving the storability of the image. Accompany it. For example, a hardening bath to prevent excessive softening of the photosensitive film during processing, a stopping bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a removing bath to remove the backing layer of the support. A process such as a membrane bath may be mentioned.

In order to introduce the coupler into the silver halide photographic light-sensitive material of the present invention, the conventionally known method for adding or dispersing the coupler to the emulsion and its addition method to the gelatin / silver halide emulsion or hydrophilic colloid are known. Is applied. For example, a high-boiling organic solvent-dibutyl phthalate, tricresyl phosphate, wax, a method of mixing and dispersing a coupler with a higher fatty acid and its ester, for example, U.S. Pat.
304,939, No. 2,322,027, etc. Also, a method in which a coupler having a low boiling point organic solvent or a water-soluble organic solvent is mixed and dispersed. A method of dispersing the coupler in combination with a high boiling point organic solvent. For example, U.S. Pat.
No. 0, No. 2,801,171, No. 2,949,360, etc., the coupler itself is sufficiently low melting point (for example, 75 ℃
In the case of the following), a method of dispersing them alone or in combination with other couplers to be used in combination, such as colored couplers or uncolored couplers. For example German Patent No. 1,14
Descriptions such as 3,707 apply.

As the dispersion aid, a commonly used anionic surfactant (for example, alkylbenzene sodium sulfonate,
Sodium dioctyl sulfosuccinate, sodium dodecyl sulphate, sodium alkylnaphthalene sulfonate, Fischer type couplers, etc. Zwitterionic surfactants (eg N-tetradecyl N, N dipolyethylene α betaine etc.) and nonionic surfactants (For example, sorbitan, monolaurate, etc.) is used.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, a color-forming coupler, that is, a color formed by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in the color development processing is formed. It may also contain a compound. For example, magenta couplers include 5-pyrazolone couplers, virazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides). , Etc., and cyan couplers include naphthol couplers, phenol couplers, and the like. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, it may be a colored coupler having a color correcting effect, or a coupler releasing a development inhibitor with development (so-called DIR coupler). In addition to the DIR coupler, a colorless DIR coupling compound which is colorless in the product of the coupling reaction and releases a development inhibitor may be contained.

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, it is a peel-apart type or Japanese Patent Publication No.
16356, 48-33697, JP-A-50-13040 and British Patent 1,330,524, integrated type, peeling as described in JP-A-57-119345 The unnecessary film unit can be configured.

The compounds of the present invention can also be used in black-and-white light-sensitive materials. Examples of the black-and-white light-sensitive material include X-ray film for direct medical use, black-and-white film for general photography, lith film, scanner film and the like.

Other constitutions of the silver halide photographic light-sensitive material of the present invention, for example, 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 the curing agent, hydrophilic colloid binder, matting agent, dye, sensitizing dye, anti-fading agent, anti-color mixing agent, polymer latex, whitening agent, antistatic agent, etc., for example Research Disclosure (Research Disclosur) Volume 176, 22-31
The description on page (December 1978) can be referred to.

Further, a method of exposing the silver halide photographic light-sensitive material of the present invention,
The developing method and the like are not particularly limited, and for example, Research. Any of known methods and known processing solutions such as those described in Disclosure, pages 28 to 30, can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually selected between 18 ° C and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C.

The developing solution used for black-and-white photographic processing may contain a known developing agent. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-
Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p)
-Aminophenol) and the like can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, etc.,
Further, if necessary, a dissolution aid, a color toning agent, a development accelerator, a surfactant, a defoaming agent, a water softener, a film hardener, a viscosity imparting agent, etc. may be contained.

A so-called "lith type" development process can be applied to the photographic emulsion of the present invention. What is "lith type" development processing? For the photographic reproduction of line images or the photographic reproduction of halftone images with halftone images, dihydroxybenzenes are usually used as the developing agent, and the development process is performed under a low sulfite ion concentration. It is a development process that makes the process contagious.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known general aromatic amine developers such as phenylenediamines (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-
Methanesulfoamidoethylaniline, 4-amino-3-
Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

LFA Mason's "Photo Processing Chemistry" (published by Focal Press) [LFAMason, Photographic Processing Ch
emistry (Focal Press)], pp. 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364, JP-A-48-64933.
No., etc. may be used.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (IV), chromium (VI) and copper (II), peracids, quinones and nitroso compounds are used.

(Effects of the Invention) The silver halide photographic light-sensitive material of the present invention has an excellent effect that it stably exists under storage conditions and promptly and efficiently releases a photographic reagent at a timing required during processing. Play. In particular, the silver halide photographic light-sensitive material of the present invention can realize a timely release of the photographic reagent even when it is processed with a processing solution having a relatively low pH of 9 to 12. The silver halide photographic light-sensitive material of the present invention releases a photographic reagent in a timely manner by performing an ordinary heat development treatment even when the heat development treatment is performed. Further, in the present invention,
By adding a photographic reagent precursor, it is possible to prevent desensitization and to exert the function of the released photographic reagent.

(Examples) Hereinafter, the present invention will be described in more detail based on specific examples, but the present invention is not limited thereto.

Example 1 In order to evaluate the compounds of the present invention and their control (comparative) compounds for the effectiveness of the antifoggant precursors of the present invention, a first sublayer was provided on a cellulose triacetate film support provided with a subbing layer. Dissolving and emulsifying the antifoggant shown in the table and the blocked antifoggant (antifoggant precursor) of the present invention in a tricresyl phosphate together with a coupler (Cp-1), and coating an emulsion layer added. Samples A to F were prepared in accordance with. The coating amount of each substance is shown in parentheses as g / m ² or mol / m ² .

(1) Emulsion layer Negative type silver iodobromide emulsion, grain size 1.4μ (silver 1.6 × 10 ^-2
mol / m ² ) Magenta coupler Cp-1 (1.3 × 10 ^-3 mol / m ² ) Antifoggant or its precursor (specified in Table 1) Gelatin (2.50g / m ² ) (2) Protective layer Gelatin (1.30) g / m ²⁾ 2,4- dichloro-6-hydroxy -s- triazine sodium salt (0.05g / m ²⁾ using a tungsten light source of the photographic element, the exposure of 25CMS adjusting the color temperature to 4800 ° K with a filter After giving
Development processing was performed at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each process is as follows. It was

Color developer Diethyleneamine pentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.0 mg Hydroxylamine sulfate 2.4 g 4- (N -Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5 g Water added 1.0 pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediamminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water added 1.0 pH6.0 Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water is added 1.0 pH6.6 Stabilizing solution Formalin (40%) 2.0 ml Poly Oxyethylene-p-monononylphenyl ether (average degree of polymerization ≈10) 0.3 g Water was added 1.0 The photographic properties of the thus treated product are shown in Table 1.

From Table 1, in Samples B to D using the precursor compound of the present invention, fog is reduced with almost no decrease in sensitivity. On the other hand, in Sample E using the precursor compound described in JP-B-55-34927, the fog is reduced, but the sensitivity is greatly reduced. Further, in the sample F containing the antifoggant, the sensitivity was remarkably lowered.

Therefore, the antifoggant precursor of the present invention is stably present in the photographic element film, and by releasing the antifoggant during processing, fog can be specifically reduced without desensitization. .

Comparative antifoggants and couplers used herein are as follows.

Example 2 To evaluate the compounds of the present invention and their control (comparative) compounds for the effectiveness of the auxiliary developer precursors in the present invention, a second sublayer was provided on a cellulose triacetate film support provided with a subbing layer. Samples FJ were prepared by coating the emulsion layers prepared by dissolving and emulsifying the auxiliary developing agents and their precursors shown in the table together with the coupler (Cp-1) in tricresylphosphate.
The coating amount of each substance is shown in parentheses as g / m ² or mol / m ² .

(1) Emulsion layer Negative type silver iodobromide emulsion, grain size 1.4μ (silver 1.6 × 10 ^-2
mol / m ² ) Magenta coupler Cp-1 (1.33 × 10 ^-3 mol / m ² ) Auxiliary developer or its precursor (1.33 × 10 ^-3 mol / m ² )
m ² ) Gelatin (2.50 g / m ² ) (2) Protective layer Gelatin (1.30 g / m ² ) 2,4-dichloro-6-hydroxy-s-triazine sodium salt (0.05 g / m ² ) These film samples At 40 ° C and 70% relative humidity
After standing for 14 hours, imagewise exposure for sensitometry was applied and the same color development process as in Example 1 was performed.

The photographic properties of the thus obtained product are shown in Table 2.

As is clear from Table 2, fog is increased and desensitized in the sample to which the auxiliary developing agent is added as it is, but in the samples H and I using the compound of the present invention, fog is hardly increased and sensitized.

The auxiliary developers 2-A and 2-B used here are as follows.

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer, which is represented by the following general formula [I]:
A silver halide photographic light-sensitive material containing at least one photographic reagent precursor represented by General formula [I] (Wherein R ₁ represents a hydrogen atom or a substituent; Y represents an oxygen atom or = NR ₂ (R ₂ represents a substituent); T represents a timing group; L represents a linking group; X Represents an electrophilic center; PUG forms an oxygen atom, a sulfur atom or a ring,
And a photographically useful group in which at least one of the adjacent atoms is a nitrogen atom, which is a nitrogen atom; m represents 0 or 1, and n represents 0 or 1. When m is 1, Y and X are bonded to each other via 3 to 5 atoms. )