JPH07119970B2 - Image forming method - Google Patents

Description

The present invention relates to a method for processing a silver halide photographic light-sensitive material,
More specifically, it relates to a method of processing a photographic light-sensitive material containing a light-sensitive silver halide emulsion layer in combination with a blocked photographic reagent releasing a photographically useful reagent.

(Prior Art) Adding a photographically useful photographic reagent to a photographic light-sensitive material in advance and exerting its effect has a characteristic different from that when it is used by being contained in a processing solution. . As its characteristic, for example, it is possible to effectively use a photographic reagent that is easily decomposed under acid / alkali or oxidation / reduction conditions and does not withstand long-term storage in a processing bath, and at the same time simplifies the composition of the processing solution and facilitates adjustment. Or, it becomes possible to activate the required photographic reagent at the required timing during processing, or it is also possible to activate the required photographic reagent only in the required place, that is, only in a specific layer of the multilayer photosensitive material and a layer in the vicinity thereof. , The amount of photographic reagent present can be varied as a function of silver halide development, and the like. 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 or be decomposed by the influence of heat or oxygen during storage before processing. Therefore, the expected performance cannot be achieved during processing. One method for solving such a problem is to block the active groups of the photographic reagent and add it to the photographic light-sensitive material as a substantially inactive form, that is, as a photographic reagent precursor. When a useful photographic reagent is a dye, 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, a halogen having a corresponding photosensitive spectral region is obtained. Even if the silver halide emulsion layer and the silver halide emulsion layer coexist in the same layer, there is an advantage that the so-called filter effect does not cause a reduction in sensitivity. If a useful photographic reagent is an antifoggant or a development inhibitor, blocking the active group can suppress the desensitization effect due to adsorption to the photosensitive silver halide during storage and silver salt formation, and at the same time, it is necessary. By releasing these photographic reagents at various timings, 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, or fogging agents, blocking active or adsorptive groups prevents various photographic adverse effects due to formation of semiquinone or oxidant due to air oxidation during storage. Alternatively, there is an advantage that the generation of fog nuclei during storage is prevented by preventing electron injection into silver halide, and as a result, stable processing can be realized. The photographic reagent is a bleach accelerator or bleach
Also in the case of fixing accelerators, by blocking their active groups, the reaction with other components contained in them is suppressed during storage, and by removing the block groups during processing, the desired performance is obtained at the required time. It has the advantage that it can be fully utilized. In the present invention, the above-mentioned active group, functional group and adsorption group are collectively referred to as "active group".

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 strict requirements. There must be. That is, it exists stably under storage conditions,
At the time of processing, it is necessary to satisfy the contradictory requirements that the block group is released at a required timing to release the photographic reagent promptly and efficiently.

Examples of the block group may include some known ones.

For example, JP-B-48-9968, JP-A-52-8,828, and JP-A-57-8
2,834, US Pat. No. 3,311,476, Japanese Patent Publication No. 47-44,805 (US Pat. No. 3,615,617) acyl groups,
Using a block group such as sulfonyl group;
-17,369 (US Patent 3,888,677), 55-9,696 (US Patent 3,791,830), 55-34,927 (US Patent 4,009,
No. 029), JP-A-56-77,842 (US Pat. No. 4,307,175)
Nos. 59-105,642 and 59-105,640, utilizing a block group which releases a photographically useful reagent by the so-called reverse Michael reaction, JP-B-54-39,727, U.S. Pat.
3,674,478, No. 3,932,480, No. 3,993,661, JP-A-57-135,944, 57-135,945, with the formation of quinone methide or quinone methide compounds by intramolecular electron transfer described in 57-136,640. Utilizing a block group that releases a photographically useful reagent; JP-A-55-53,330 and 59-21
Utilizing the intramolecular ring closure reaction described in 8,439; JP-A-57-76,541 (Japanese Patent No. 4,335,200) and 57-135,949.
No. 57, No. 57-179,842, No. 59-137,945, No. 59-140,445
Nos. 59-219,741 and 60-41,034, which utilize the 5- or 6-membered ring cleavage are known as known techniques.

According to these known techniques, the release rate of the photographic reagent is too small at the time of processing if it is stable under storage conditions, and a high alkali treatment of pH 12 or more is required, or the release rate is high in a processing solution of pH 9 to 12. Even if it is sufficient, it has the drawback of gradually decomposing under storage conditions and impairing its function as a precursor. These drawbacks can be attributed to relying on the attack of OH ^- ions to release the photographically useful reagent from the blocked photographic reagent. That is, at a pH of 9 to 12 in the development of a conventional photographic light-sensitive material,
The difference in OH ⁻ ion concentration between storage and processing of the photographic light-sensitive material is 10 ² to 10 ⁵ due to the pH of 6 to 7 during storage. Therefore, for example, a blocked photographic reagent that releases a photographically useful reagent with a half-life of 3 minutes (half of the added amount takes 3 minutes to decompose) when treated at pH 10 is stored (at pH = 6 ) It is estimated that it decomposes with a half-life of 3 minutes × 10 ⁴ = 30,000 minutes ≈ 500 hours. This means that half of the used amount is decomposed by storage for about 3 weeks, and it is not practically usable at all. Similarly, in the case of pH11 treatment, the block compound that releases with a half-life of 3 minutes during treatment has a half-life of 10 times, which is about 30 weeks for degradation during storage, but this is a very unsatisfactory number, and storage stability is long. Therefore, it can be said that practical use is difficult.

OH release of photographically useful reagents from blocked photographic reagents
^- Another problem attributable to that Yoriyukitsu the ion attacks include that decrease in emission efficiency of photographically useful reagent. That is, at the same time as the desired reaction for releasing the photographically useful reagent, an unexpected side reaction occurs, and the blocked photographic reagent is killed without releasing the photographically useful reagent, for example, U.S. Pat.No. 4,135,929. Book, Journal of Organic Compounds, 39, 331, 1981, 40
Vol. 176, 1982 etc. Such a decrease in the release efficiency not only increases the amount of the blocked photographic reagent used, but also causes substantial photographic adverse effects due to a by-product often generated by an unexpected side reaction, which substantially causes substantial deterioration. The intended purpose may not be achieved and thus such blocked photographic reagents may become unusable.

A block group for solving such a problem is disclosed in Japanese Patent Laid-Open No. 59-2.
01,057, Japanese Patent Application No. 59-145,593, Japanese Patent Application No. 59-216,926,
It is known to utilize a block group which releases a photographically useful group by adding a nucleophile to an unsaturated bond described in JP-A-59-216928.

However, even in such a block group, when the bond to be cleaved is a carbon-nitrogen bond or a carbon-oxygen bond, the release rate of the photographically useful reagent may be small during processing, and a technique for further improvement is desired. Was there.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to achieve stability under storage conditions and timing at the time of processing, which are the most difficult points in utilizing a precursor compound of a photographically useful reagent. Another object is to provide a general method with high versatility that can satisfy the contradictory requirements of ensuring the release of photographically useful reagents.

A second object of the present invention is to provide a method capable of achieving a timely release of a photographic reagent even at a relatively low pH of 9-12.

A third object of the present invention is to provide a general method for suppressing side reactions and increasing the release efficiency of photographically useful reagents.

A fourth object of the present invention is to improve the black spots of a photographic light-sensitive material capable of forming a super-high contrast negative image with a stable developer by the action of a hydrazine derivative.

(Means for Solving the Problems) An object of the present invention is to provide a photosensitive halogenated compound in which at least one blocked photographic reagent represented by the general formula (I) which releases a development inhibitor is combined with a hydrazine derivative. A photographic light-sensitive material containing a silver emulsion layer is imagewise exposed and then processed in the presence of dihydroxybenzenes and / or aminohydroxybenzenes.

General formula (I) (In the formula, X ¹ represents a divalent linking group bonded to C through a nitrogen atom or an oxygen atom, and PUG represents a development inhibitor bonded to X ¹ through a hetero atom of PUG. , R ¹ , R ² and R ³ represent a hydrogen atom or a substitutable group, and R ¹ and R ² and R ¹ and R ³ may combine to form a carbocycle or a heterocycle.

A cyano group or a nitro group (wherein R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom or a substitutable group), and n and m
Represents 0 or 1. However, when m = 0, the development inhibitor represented by PUG binds to C at the nitrogen atom or oxygen atom of PUG.

The present invention has hitherto been directed to a method capable of releasing the above photographically useful reagents.
Is it a photographic reagent (a useful photographic reagent precursor)?
Release OH I skipped the fault by relying on Aeon
To provide a means of accelerating release that can be dramatically improved,
Release, at least in the precursor compounds mentioned above
The purpose is achieved regardless of the types of photographically useful reagents used.
Sent.

Dihydroxybenzenes or aminohydroxybenzes
Of various photographic properties from precursor compounds, for example.
The release of the chemical reagent significantly, or its release effect
The fact that the rate increases dramatically is totally unexpected
Yes, the detailed reason for its effect is currently unknown
However, the release rate of the photographically useful reagent from the precursor compound
Degree is OH Occurs in nucleophilic reactions with ions and subsequent reactions
The fact that there is a significant increase compared to the case
Xybenzenes or aminohydroxybenzenes, eg
For example, the compound represented by the general formula (IV) is OH Ion's request
It has significantly increased nuclear capacity, or OH ion
In lieu of these compounds undergoing a nucleophilic attack,
Nucleophilic ability is OH It is overwhelmingly larger than Ion,
It is speculated that both effects are working. Either
However, the expression of such a remarkable acceleration effect is
Conflicting requirements for using sir compounds, namely
Storage stability and deblocking with good timing during processing
A means that can solve the difficult task of ensuring (release)
Provided, especially at relatively low pH (9-12)
The effect is particularly large in the processing of ordinary sensitive materials
It can be said that it will be demonstrated. Normal photosensitive material here means development start
Halogenation with development center in front (latent image or fog nucleus)
The image is obtained by reducing silver particles with a developing agent that follows the pelz rule.
An image forming material other than the diffusion transfer method.

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

R ¹ represents a hydrogen atom or a substitutable group, and as the substitutable group, an alkyl group (preferably having 1 to 20 carbon atoms), an alkenyl group (preferably having 2 to 20 carbon atoms), an aryl group ( Preferably having 6 to 20 carbon atoms),
Alkoxy group (preferably having 1 to 20 carbon atoms), aryloxy group (preferably having 6 to 20 carbon atoms), alkylthio group (preferably having 1 to 20 carbon atoms), arylthio group (preferably having carbon number) 6-20), an amino group (unsubstituted amino, preferably a secondary or tertiary amino group substituted with an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms), a hydroxy group, etc. These substituents may have one or more of the following substituents, and when there are two or more substituents, they may be the same or different.

Here, as a specific substituent, a halogen atom (fluorine, chlorine, bromine), an alkyl group (preferably having a carbon number of 1 to 1)
20), aryl group (preferably having 6 to 20 carbon atoms), alkoxy group (preferably having 1 to 20 carbon atoms), aryloxy group (preferably having 6 to 20 carbon atoms), alkylthio group (Preferably having 1 to 20 carbon atoms), arylthio group (preferably having 6 to 20 carbon atoms), acyl group (preferably having 2 to 20 carbon atoms), acylamino group (preferably having 1 to 20 carbon atoms) Alkanoylamino group, benzoylamino group having 6 to 20 carbon atoms), nitro group, cyano group, oxycarbonyl group (preferably alkoxycarbonyl group having 1 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms), Hydroxy group, carboxy group, sulfo group, ureido group (preferably having 1 to 20 carbon atoms)
Alkyl ureido group, an aryl ureido group having 6 to 20 carbon atoms), a sulfonamide group (preferably an alkyl sulfonamide group having 1 to 20 carbon atoms, an aryl sulfonamide group having 6 to 20 carbon atoms), a sulfamoyl group (preferably C1-C20 alkylsulfamoyl group, C6-C20 arylsulfamoyl group, carbamoyl group (preferably C1-C20 alkylcarbamoyl group, C6)
~ 20 arylcarbamoyl group), an acyloxy group (preferably having 1 to 20 carbon atoms), an amino group (unsubstituted amino, preferably an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms) Substituted secondary or tertiary amino group), carbonic acid ester group (preferably alkyl carbonic acid ester group having 1 to 20 carbon atoms, aryl carbonic acid ester group having 6 to 20 carbon atoms), sulfone group (preferably having 1 to 1 carbon atom) Examples thereof include an alkylsulfone group having 20 carbons, an arylsulfone group having 6 to 20 carbons, and a sulfinyl group (preferably an alkylsulfinyl group having 1 to 20 carbons and an arylsulfinyl group having 6 to 20 carbons). it can.

Further, R ¹ may combine with R ² or R ³ to form a carbocycle or a heterocycle (for example, a 5- to 7-membered ring). R ² and R ³ may be the same or different and each represents a hydrogen atom or a substitutable group, and as the substitutable group, a halogen atom (fluorine, chlorine, bromine), an alkyl group (preferably having 1 to 1 carbon atoms).
20), aryl group (preferably having 6 to 20 carbon atoms), alkoxy group (preferably having 1 to 20 carbon atoms), aryloxy group (preferably having 6 to 20 carbon atoms), alkylthio group (Preferably having 1 to 20 carbon atoms), arylthio group (preferably having 6 to 20 carbon atoms), acyloxy (preferably having 2 to 20 carbon atoms), amino group (unsubstituted amino, preferably carbon number) 1 to
A 20-alkyl group, or a secondary or tertiary amino group substituted with an aryl group having 6 to 20 carbon atoms, a carbonamido group (preferably an alkylcarbonamide group having 1 to 20 carbon atoms, a carbon atom having 6 to 20 carbon atoms) Aryl carbonamide group), ureido group (preferably alkyl ureido group having 1 to 20 carbon atoms, aryl ureido group having 6 to 20 carbon atoms), carboxy group, carbonic acid ester group (preferably alkyl carbonic acid ester having 1 to 20 carbon atoms) Group, an aryl carbonate group having 6 to 20 carbon atoms, an oxycarbonyl group (preferably having 1 to 20 carbon atoms)
Alkyloxycarbonyl group, C6-20 aryloxycarbonyl group), carbamoyl group (preferably C1-20 alkylcarbamoyl group, C6-20)
Arylcarbamoyl group), an acyl group (preferably an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group having 6 to 20 carbon atoms), a sulfo group, a sulfonyl group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, Carbon number 6
To 20 arylsulfonyl group), a sulfinyl group (preferably an alkylsulfinyl group having 1 to 20 carbon atoms, an arylsulfinyl group having 6 to 20 carbon atoms), a sulfamoyl group (preferably an alkyl group having 1 to 20 carbon atoms) Sulfamoyl group, arylsulfamoyl group having 6 to 20 carbon atoms), cyano group and nitro group.

The substituents represented by R ² and R ³ may have one or more substituents, and when there are two or more substituents, they may be the same or different, and specific substituents are the same as those mentioned above. ^The same as the substituent of ¹ can be mentioned.

It represents a cyano group or a nitro group, and R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or a substitutable group, and a specific substituent is an alkyl group (preferably a carbon number). 1-20), alkenyl group (preferably having 2-20 carbon atoms), aryl group (preferably having 6-20 carbon atoms), alkoxy group (preferably having 1-20 carbon atoms), aryl Oxy group (preferably having 6 to 20 carbon atoms), acyloxy group (preferably having 2 to 20 carbon atoms), amino group (unsubstituted amino group, preferably alkyl group having 1 to 20 carbon atoms, or carbon number Secondary or tertiary amino group substituted with an aryl group having 6 to 20), carbonamide group (preferably alkylcarbonamide group having 1 to 20 carbon atoms, arylcarbonamide group having 6 to 20 carbon atoms), ureido group ( Preferred Is an alkylureido group having 1 to 20 carbon atoms, an arylureido group having 6 to 20 carbon atoms), an oxycarbonyl group (preferably an alkyloxycarbonyl group having 1 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms) , A carbamoyl group (preferably having a carbon number of 1 to
20 alkylcarbamoyl group, C6-20 arylcarbamoyl group), acyl group (preferably C1-20)
Alkylcarbonyl group, arylcarbonyl group having 6 to 20 carbon atoms, sulfonyl group (preferably alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 20 carbon atoms), sulfinyl group (preferably having 1 carbon atom) To 20 alkylsulfinyl groups, C6 to C20 arylsulfinyl groups), sulfamoyl groups (preferably 1 carbon atoms)
˜20 alkylsulfamoyl group and C 6-20 arylsulfamoyl group). These substituents are 1
It may have one or more substituents, and when there are two or more substituents, they may be the same or different, and specific substituents include the same as the above-mentioned substituents for R ¹ .

Specific examples of R ₁ and R ₃ or R ₁ and R ₂ bonded to each other to form a carbocycle or a heterocycle include the following general formulas (II) and (III)
The following can be mentioned.

General formula (II) General formula (III) In the general formula (II), Z ¹ represents an atomic group necessary for forming a carbocycle or a heterocycle.

Specifically, for example, a 5-membered, 6-membered, or 7-membered carbon ring, or a 5-membered, 6-membered, or 7-membered heterocycle containing one or more nitrogen, oxygen, or sulfur atoms. And these carbocycles or heterocycles also include those forming a condensed ring at an appropriate position.

Specifically, cyclopentenone, cyclohexenone, cycloheptenone, benzocycloheptenone, benzocyclopentenone, benzocyclohexenone, 4-pyridone, 4-quinolone, 2-pyrone, 4-pyrone, 1-thio-2- Pyrone, 1-thio-4-pyrone, coumarin, chromone, uracil, etc. And so on. Here, these carbocycles or heterocycles may have one or more substituents, and when there are two or more substituents, they may be the same or different. Specific examples of the substituent include the same as the above-mentioned substituents of R ¹ .

Further, Z ² in the general formula (III) means the same as Z ^{1 in the} general formula (II), specifically, cyclopentanone, cyclohexanone, cycloheptanone, benzocycloheptanone, benzocyclopentanone, Examples thereof include benzocyclohexanone, 4-tetrahydropyridone, 4-dihydroquinolone and 4-tetrahydropyrone. These carbocycles or heterocycles may have one or more substituents,
When there are two or more substituents, they may be the same or different. Specific examples of the substituent include the same as the above-mentioned substituent of R ¹ .

R ² , R ³ , X ^1, PUG and m are the same as those mentioned in the general formula (I).

Next, even if the photographically useful reagent is directly bonded through a nitrogen atom or an oxygen atom in the photographically useful reagent (m = 0),
Alternatively, it may be bonded via X ¹ (m = 1) X ¹ represents a divalent linking group, and is bonded via a nitrogen atom or an oxygen atom in the linking group, and during treatment (more specifically, (Under the condition of pH 9-12) as X ¹ -PUG,
Represents a group that rapidly releases PUG.

Examples of such a connecting group include JP-A-54-145135 (UK Patent Publication No. 2,010,818A) and US Pat. No. 4,248,962.
No. 4,409,323, which releases PUG by an intramolecular ring closure reaction described in British Patent No. 2,096,783, British Patent No. 2,0
72,363, those releasing PUG by intramolecular electron transfer described in JP-A-57-154,234, JP-A-57-179,84
No. 2 etc. releasing PUG with carbon dioxide desorption, or those releasing PUG with formalin elimination described in JP-A-59-93422, and the like. You can The representative X ¹ described above is shown below together with their structural formulas PUG.

What is used as X ¹ is selected and used according to the timing of PUG release, the control of release, the type of PUG used, and the like.

Examples of development inhibitors represented by PUG include compounds having a mercapto group bonded to a heterocycle, such as substituted or unsubstituted mercaptoazoles (specifically, 1-phenyl-5-mercaptotetrazole, 1- (4-carboxyl Phenyl) -5-mercaptotetrazole, 1- (3-
Hydroxyphenyl) -5-mercaptotetrazole,
1- (4-sulfophenyl) -5-mercaptotetrazole, 1- (3-sulfophenyl) -5-mercaptotetrazole, 1- (4-sulfamoylphenyl) -5
-Mercaptotetrazole, 1- (3-hexanoylaminophenyl) -5-mercaptotetrazole, 1-ethyl-5-mercaptotetrazole, 1- (2-carboxyethyl) -5-mercaptotetrazole, 2-methylthio-5- Mercapto-1,3,4-thiadiazole, 2
-(2-Carboxyethylthio) -5-mercapto-1,
3,4-thiadiazole, 3-methyl-4-phenyl-5
-Mercapto-1,2,4-triazole, 2- (2-dimethylaminoethylthio) -5-mercapto-1,3,4-thiadiazole, 1- (4-n-hexylcarbamoylphenyl) -2-mercapto Imidazole, 3-acetylamino-4-methyl-5-mercapto-1,2,4-triazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercapto-6-nitro-1. , 3-Benzoxazole, 1- (1-naphthyl) -5-mercaptotetrazole, 2-phenyl-5-mercapto-1,3,4-
Oxadiazole, 1- {3- (3-methylureido)
Phenyl} -5-mercaptotetrazole, 1- (4-
Nitrophenyl) -5-mercaptotetrazole, 5-
(2-ethylhexanoylamino) -2-mercaptobenzimidazole, etc., and substituted or unsubstituted mercaptoazaindenes (specifically, 6-methyl-4-mercapto-1,3,3a, 7-tetrazaine Den, 6-methyl-
2-benzyl-4-mercapto-1,3,3a, 7-tetrazaindene, 6-phenyl-4-mercaptotetrazaindene, 4,6-dimethyl-2-mercapto-1,3,3a, 7-tetra Such as zindene), substituted or unsubstituted mercaptopyrimidines (specifically, 2-mercaptopyrimidine,
2-mercapto-4-methyl-6-hydroxypyrimidine, 2-mercapto-4-propylpyrimidine and the like). Heterocyclic compounds capable of producing imino silver, for example, substituted or unsubstituted benzotriazoles (specifically, benzotriazole, 5-nitrobenzotriazole, 5-methylbenzotriazole, 5,6-dichlorobenzotriazole, 5- Bromobenzotriazole, 5
-Methoxybenzotriazole, 5-acetylaminobenzotriazole, 5-n-butylbenzotriazole, 5-nitro-6-chlorobenzotriazole, 5,6
-Dimethylbenzotriazole, 4,5,6,7-tetrachlorobenzotriazole, etc.) Substituted or unsubstituted indazoles (specifically, indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5-
Nitroindazole, 3-cyanoindazole, 3-n
-Butylcarbamoylindazole, 5-nitro-3-
Methanesulfonylindazole, etc.), substituted or unsubstituted benzimidazoles (specifically, 5-nitrobenzimidazole, 4-nitrbenzimidazole,
5,6-dichlorobenzimidazole, 5-cyano-6-
Chlorbenzimidazole, 5-trifluoromethyl-
6-chlorobenzimidazole) and the like.

Further, the development inhibitor is used in the development process in the general formula (I).
After being released from the mother nucleus of the above, it becomes a compound having a development inhibiting property. The compound may then be converted to a compound which has substantially no development inhibiting properties or is significantly reduced.

Specifically, 1- (3-phenoxycarbonylphenyl)
-5-mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5-mercaptotetrazole,
1- (3-maleinimidophenyl) -5-mercaptotetrazole, 5- (phenoxycarbonyl) benzotriazole, 5- (p-cyanophenoxycarbonyl)
Benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 5-
Nitro-3-phenoxycarbonylindazole, 5-
Phenoxycarbonyl-2-mercaptobenzimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 5-benzyloxycarbonylbenzotriazole, 5- (butylcarbamoylmethoxycarbonyl) benzotriazole, 5- (butoxy Carbonylmethoxycarbonyl) benzotriazole,
1- (4-benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 1-
{4- (2-chloroethoxycarbonyl) phenyl}-
2-Mercaptoimidazole, 2- [3- {thiophen-2-ylcarbonyl} propyl] thio-5-mercapto-1,3,4-thiadiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) (Enyl) -5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2- {4-succinimidophenyl} -5-mercapto-1,3,4-oxadiazole, 3- {4- (benzo-1,2) -Isothiazole-
3-oxo-1,1-dioxy-2-yl) phenyl}-
5-mercapto-4-methyl-1,2,4-triazole,
6-phenoxycarbonyl-2-mercaptobenzoxazole and the like can be mentioned.

Next, the dihydroxybenzenes and aminohydroxybenzenes used in the present invention will be described. A preferred example is represented by the following general formula (IV).

General formula (IV) In the formula, R ⁷ represents a hydrogen atom or a group capable of being cleaved by an alkali component or other components of the treatment liquid during treatment, or a group capable of forming a counter ion with an oxygen anion, and the like, a dihydroxybenzene structure during treatment. Or containing all groups capable of forming an aminohydroxybenzene structure,
X ² represents OR ⁷ or NR ¹² R ¹³ (R ¹² and R ¹³ may be the same or different and each is a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an aryl group. A carbonyl group, which may be substituted.) R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different and each represents a hydrogen atom or a substitutable group, R ⁸ and R ⁹ combined and 5
~ 7-membered carbocycles or heterocycles may be formed and these rings may be saturated or unsaturated.

More preferable specific examples among the compounds represented by the general formula are as follows.

R ⁷ is a hydrogen atom or an acyl group (preferably having 2 to 20 carbon atoms), and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are hydrogen atoms, halogen atoms (fluorine, chlorine, bromine), alkyl groups ( Preferably having 1 to 20 carbon atoms), aryl group (preferably having 6 to 20 carbon atoms), alkoxy group (preferably having 1 to 20 carbon atoms)
20), aryloxy group (preferably having 6 to 6 carbon atoms)
20), alkylthio group (preferably having 1 to 20 carbon atoms)
Group), an arylthio group (preferably having 6 to 20 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms),
Acylamino group (preferably alkanoylamino group having 1 to 20 carbon atoms, benzoylamino group having 6 to 20 carbon atoms), nitro group, cyano group, oxycarbonyl group (preferably alkoxycarbonyl group having 1 to 20 carbon atoms, carbon number 6-20 arylcarbonyl group), hydroxy group, carboxy group, sulfo group, ureido group (preferably alkyl ureido group having 1 to 20 carbon atoms, aryl ureido group having 6 to 20 carbon atoms), sulfonamide group (preferably Alkyl sulfonamide group having 1 to 20 carbon atoms, aryl sulfonamide group having 6 to 20 carbon atoms, sulfamoyl group (preferably alkyl sulfamoyl group having 1 to 20 carbon atoms, aryl sulfamoyl group having 6 to 20 carbon atoms) Group), a carbamoyl group (preferably an alkylcarbamoyl group having 1 to 20 carbon atoms, a carbon number of 6 to
20 arylcarbamoyl group), an acyloxy group (preferably having 1 to 20 carbon atoms), an amino group (unsubstituted amino, preferably an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms) A secondary or tertiary amino group), a carbonic acid ester group (preferably an alkyl carbonic acid ester group having 1 to 20 carbon atoms, an aryl carbonic acid ester group having 6 to 20 carbon atoms), a sulfone group (preferably 1 to 20 carbon atoms). And an alkylsulfone group having 6 to 20 carbon atoms) and a sulfinyl group (preferably an alkylsulfinyl group having 1 to 20 carbon atoms and an arylsulfinyl group having 6 to 20 carbon atoms). .

Examples of the ring-forming compound in which R ⁸ and R ⁹ are bonded to each other include cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexadiene, cycloheptadiene, indane, norbornane, norbornene, pyridine, and the like. May have.

Among those represented by the general formula (IV), X ² is particularly preferably OR ⁷ .

The compound represented by the general formula (IV) may be added to the processing solution and used, or may be added to the photosensitive material in advance and used. When added to the treatment liquid, it is particularly preferable that R ^{8 to} R ^{11 have} a total carbon number of 1 to 10 from the viewpoint of solubility. When added to the light-sensitive material, the carbon number is not particularly limited, but if it is desired to release the photographically useful reagent only in a specific layer of the light-sensitive material, R ^{7 to} R
^11, of the type group is loosely ballasted said represented by X ² (specifically R ⁷ to R ^11, the total number of carbon atoms of X ² is 10 or more, or at least one 10 or more) may be used to .

Specific examples of the general formula (I) used in the present invention are listed below, but the invention is not limited thereto.

Next, specific examples represented by the general formula (IV) that can be used in the present invention are listed, but the invention is not limited thereto.

In addition to these compounds, JP-A-59-201057 and Japanese Patent Application No. 59-21
The compounds described in 6926 and 59-216928 can also be used in the present invention.

The precursor compound represented by the general formula (I) is disclosed in the above-mentioned patent specifications (particularly JP-A-59-201057, Japanese Patent Application No. 59-21).
No. 6926, No. 59-216928).

On the other hand, the synthesis of the compound represented by the general formula (IV) is described in West German Patent No. 2,110,521 and French Patent No. 1,496,562.

The precursors 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 of silver halide photographic light-sensitive material, color material layer, undercoat layer, protective layer, intermediate layer, filter layer, antihalation layer, image receiving layer, cover sheet layer, neutralizing layer, neutralizing timing layer, It may be added to any of the white reflective layer and other auxiliary 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. Also, by dissolving the precursor in a high boiling organic solvent and / or a low boiling organic solvent,
It is also possible to add it by emulsifying and dispersing it in an aqueous solution. Also,
JP-A-51-39853, 51-59942, 54-32552, U.S. Patents
The polymer latex may be impregnated and added by the method described in 4,199,363 or the like.

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 amount of the precursor of the present invention used is 10 ^-8 to 10 per mol of silver.
^-6 mol (preferably mercapto antifoggant 10 ^-6 ~
10 ^-1 mol, and azole antifoggants such as benzotriazole are 10 ^-5 to 10 ^-1 mol).

The dihydroxybenzenes and aminohydroxybenzenes represented by the general formula (IV) used in the present invention can be used in addition to a treatment liquid such as a phenomenon liquid, and those having a large carbon number can be used in advance as a sensitive material. It is also possible to add them to the above and to design them so that they are in contact with each other by diffusion in the film during processing. At this time, the compound of the general formula (IV) and the precursor are preferably added to different layers, and it is necessary to devise such that they do not come into contact with each other during coating and before treatment. Alternatively,
In the general formula (IV), R ⁷ may be used as a precursor compound having a hydrogen atom other than a hydrogen atom added to the photosensitive material.

The layer to be added may be basically any layer, but an emulsion layer,
It is preferably added to an undercoat layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer, a color material layer, an image receiving layer, a cover sheet layer and the like. On the other hand, when it is used by being added to the processing solution, it is preferably used as a development processing bath component, but in the combination with a precursor which is a bleaching or fixing accelerator as a photographically useful reagent, a post-bath after the development processing is used. (For example, a bleaching bath, a fixing bath, a bleach-fixing bath) can be added to exert the effect of the present invention.

The amount of the compound of the general formula (IV) of the present invention to be used cannot be categorically stated because it varies depending on the PUG represented by the compound of the general formula (I) to be used. , 1 × 10 ⁻⁸ to 10 mol / mol Ag. A more appropriate content is selected according to the PUG used, but the ratio of the compound of the general formula (I) / the compound of the general formula (IV) is preferably 10 ^-1 to 10 ^-3 (molar ratio). Used.

When the compound of general formula (IV) is contained in the treatment liquid, it is preferably used in an amount of 10 ⁻³ mol to 10 mol / l.

The silver halide that can be used in the present invention includes silver chloride, silver bromide,
It may be any of silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. The halogen composition in the grain may be uniform, or may have a multiple structure having different compositions on the surface and inside (JP-A-57-154232, JP-A-58-108533,
59-48755, 59-52237, U.S. Pat. No. 4,433,048 and European Patent 100,984). The particle thickness is 0.5
Tabular grains having a diameter of at least 0.6 μm and a diameter of at least 0.6 μm and an average aspect ratio of 5 or more (US Pat. No. 4,414,310;
4,435,499 and West German Open Patent (OLS) 3,241,646A1
Etc.) or a monodisperse emulsion having a nearly uniform grain size distribution (JP-A-57-178235, JP-A-58-100846, JP-A-58-14829,
WO83 / 02338A1, European Patent 64,412A3 and
83,377A1 etc.) may also be used in the present invention. Two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like may be used in combination. Gradation can also be adjusted by mixing two or more monodispersants having different particle sizes.

The grain size of the silver halide used in the present invention is preferably 0.001 μm to 10 μm, more preferably 0.001 μm.
It is more preferably from m to 5 μm. These silver halide emulsions may be prepared by any of the acidic method, the neutral method and the ammonia method, and the reaction form of the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination method thereof. Any combination of A back mixing method, in which grains are formed in the presence of excess silver ions, or a controlled double jet method, in which pAg is kept constant, can also be employed. Also,
In order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen position to be added may be increased (JP-A-55-142329, JP-A-55-158124, US Pat. No. 3,65).
0,757 etc.).

Epitaxial junction type silver halide grains can also be used (JP-A-56-16124, U.S. Pat. No. 4,094,684).
issue).

In the step of forming silver halide grains used in the present invention, ammonia as a silver halide solvent, JP-B-47-113
Organic thionite derivatives described in JP-A No. 86 or JP-A-53-1
The sulfur-containing compounds described in 44319 can be used.

Cadmium salt, zinc salt, lead salt, thallium salt and the like may be present together in the process of grain formation or physical ripening.

Further, for the purpose of improving the high illuminance failure and the low illuminance failure, water-soluble iridium salts such as iridium chloride (III, IV) and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

Soluble salts may be removed from the silver halide emulsion after formation of a precipitate or after physical ripening, and therefore the Nutel washing method or the precipitation method can be used.

The silver halide emulsion may be used as it is without ripening, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional type light-sensitive materials. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A Nos. 58-126526 and 58-215644).

The silver halide emulsion used in the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat.
2, 592,250, 3,761,276, JP-B-58-3534 and JP-A-57-136641.

The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring of these nuclei is fused; and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine nuclei, indole nuclei, benzoxadol nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benz Imidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

A dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion.

A surfactant may be added to the photographic emulsion used in the present invention alone or as a mixture.

Although they are used as coating aids, they are sometimes used for other purposes such as emulsion dispersion, improvement of sensitized photographic characteristics, antistatic, and adhesion prevention. These surfactants include natural surfactants such as saponins, nonionic surfactants such as alkylene oxides, glycerin, and glycidols, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, phosphonium or Cationic surfactant such as sulfonium, carboxylic acid, sulfonic acid, phosphoric acid, sulfate group,
An anionic surfactant containing an acidic group such as a phosphate group,
It is divided into amphoteric activators such as amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols. When used as an antistatic agent, a fluorine-containing surfactant is preferably used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxazoline thiones; azaindenes such as triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (1,3,3a, 7-tetraazaindenes), pentaazaindenes and the like; Many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amides and the like can be added.

The photographic emulsion layer of the photographic light-sensitive material of the present invention has, for example, a thioether compound, a thiomorpholine compound, a quaternary ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative, and 3-pyrazolidone for the purpose of increasing sensitivity, increasing contrast, or promoting development. You may include a class.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, acrylonitrile, olefin, styrene, etc., alone or in combination, or in combination with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, etc. as a monomer component. The polymer can be used.

The emulsion layer or auxiliary layer of the light-sensitive material of the present invention (for example, a protective layer,
As the binder that can be used in the intermediate layer), hydrophilic colloids are preferable, and gelatin is particularly advantageous, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can In addition, lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin and the like can be used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chrome salts (chromium yoban, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-). Triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycyclo acid etc.), etc. can be used alone or in combination.

Various other additives are used in the silver halide photographic light-sensitive material of the present invention. For example, whitening agents, dyes, desensitizers, coating aids, antistatic agents, plasticizers, slip agents, matting agents, development accelerators, mordants, ultraviolet absorbers, anti-fading agents,
Color antifoggant etc.

Regarding these additives, specifically, those described in RESEARCH DISCLOSURE No. 176, pages 22 to 31 (RD-17643) (Dec., 1978) and the like can be used.

The present invention is U.S. Patent Nos. 4,224,401, 4,168,977 and 4,24.
1,164, 4,311,781, 4,272,606, 4,221,857
No. 4,243,739, No. 4,272,614, No. 4,269,929, etc., a photographic light-sensitive material having a monodisperse silver halide emulsion layer capable of forming a super-high contrast negative image with a stable developer by the action of a hydrazine derivative. It is effective in improving the black spot of the material. This black spot refers to spot-like black spots (black paper) that occur in non-image areas (for example, between halftone dots), and is generally used as a preservative because the developer is exhausted at the end. It occurs remarkably when the amount of sulfite ions present decreases or when the pH of the solution becomes high, deteriorating the photographic quality. In the above, a stable developer contains sulfite ions as a preservative at least 0.15 mol / l,
Also, it means a developer having a pH of 10.0 to 12.3. Since this developing solution can contain a large amount of preservative, it is more stable than an ordinary lith developing solution (which can contain a very small amount of sulfite ion),
Since it has a relatively low pH, for example, U.S. Pat.
The developer of the high contrast image forming system described in No. 5 (pH = 12.
More stable and less susceptible to air oxidation than 8). In this case, the compound of the general formula (I) of the present invention preferably has a development inhibitor as PUG, and preferably 1 × 10 ⁻⁶ to 10 ⁻¹ mol, particularly 1 × 10 4 mol per mol of silver halide. ^-Five
It is used in the range of ˜1 × 10 ⁻¹ mol.

In the present invention, when the hydrazine derivative is contained in the photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (eg, protective layer, intermediate layer, filter layer). , An anti-halation layer, etc.). Specifically, when the compound to be used is water-soluble, as a water solution, and when it is poorly water-soluble, as a solution of an organic solvent such as alcohols, esters, and ketones that can be mixed with water, a hydrophilic colloid solution. Can be added to. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening and before coating. In particular, it is preferable to add it to the coating solution prepared for coating.

The content of these hydrazine derivatives depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, the type of antifoggant compound, etc. It is desirable to select the optimum amount by using the test method for the selection, which is well known to those skilled in the art. Usually, it is preferably used in the range of 10 ^-6 to 1 × 10 ^-1 mol, particularly 10 ^-5 to 4 × 10 ^-2 mol, per mol of silver halide.

The light-sensitive material produced by using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (for example, those described in US Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in US Pat. Nos. 3,214,794 and 3,352,681), benzophenone compounds (for example, JP-A- 46-278
No. 4), etc. may be used. These UV absorbers may be mordanted in a specific layer.

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more kinds. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

For the photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

The black-and-white developing solution contains known developing agents such as dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol) and the like. They can be used alone or in combination.

In addition, LFA Messon's "Photograph Processing Processor Chemistry", published by Focal Press (1966)
226 to 229, U.S. Patents 2,193,015 and 2,592,364,
Those described in JP-A-48-64933 may be used.

After the development, known processes such as fixing, bleaching, stabilizing, bleach-fixing, stopping and stabilizing with washing are carried out. Here, for washing with water, stabilization, etc., a method in which the amount of water is limited to a wide range may be used.

(Example) Next, the present invention will be described in detail based on examples.

Example 1 Measurement of release-accelerating effect of a photographically useful reagent from a precursor compound by various dihydroxybenzenes and aminohydroxybenzenes, precursor compound (I-
3), (I-4) and (I-7) are respectively 3.6 × 10 ⁻⁵
The mol was dissolved in 4 ml of acetonitrile and this solution was added at 25 ° C. to a mixture of 16 ml of acetonitrile and 20 ml of Britton-Robinson buffer. After a certain period of time (the buffer was adjusted in advance to pH 10.0), a certain amount of the reaction solution was lowered to pH 6.25 with acetic acid to stop the reaction, and a photographically useful reagent released by high performance liquid chromatography was used. It was quantified. The pseudo first-order reaction rate constant K'was calculated from the obtained measured values, and then the half-life t'1 / 2 was calculated. (Half-life t'1 / 2
Is the time required for half of the precursor compound to react, and was determined by t'1 / 2 = 0.693 / K '. ) Next, (IV-1) represented by the general formula (IV), (IV-1
2), (IV-26) and (IV-31) were calculated in exactly the same way except that 3.6 × 10 ^-4 mol of (IV-31) was added to 16 ml of acetonitrile in advance, and the half-life t1 / 2 was calculated. Each acceleration efficiency by Was calculated and shown in Table 1.

As shown in Table 1, when the compound of the general formula (IV) of the present invention was used in combination, a very large acceleration effect was shown.
Comparative compounds A and B similar to No. 3 did not show any accelerating effect, but showed only a very small accelerating effect.

Example 2 Measurement of the release-accelerating effect of a photographically useful reagent from a precursor compound by hydroquinone.

By the same operation as in Example 1, the acceleration effect of hydroquinone was measured for various precursor compounds and is shown in Table 2.

As shown in Table 2, it can be seen that the combined use of hydroquinone (IV-1) significantly accelerates the release of the photographically useful reagent from the precursor compound, but the comparative compounds a and b have the release function themselves. However, even if hydroquinones were used together, no acceleration effect was observed.

Example 3 Emulsions I) and II) used in the following method were prepared.

[Emulsion I]

An aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added in the presence of 4 × 10 ^-7 mol of potassium iridium (III) hexachloride and ammonia per mol of Ag to a gelatin aqueous solution kept at 50 ° C. for 60 minutes. The average grain size is 0.28μ and the average silver iodide content is 1 mol% by keeping pAg of 7.8.
A cubic monodisperse emulsion of was prepared. Further, this emulsion was washed with water according to a conventional method to remove soluble salts, and then gelatin was added. Subsequently, an emulsion I was prepared by converging the grain surface by adding an aqueous solution of 0.1 mol% potassium iodide per mol of silver.

[Emulsion II]

By adjusting the amount of ammonia in Emulsion I,
Exactly the same emulsion II having an average particle size of 0.25 μ was prepared.

In these silver iodobromide emulsions, sodium salt of 5,5'-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine was used as a sensitizing dye, and 4-hydroxy- was added as a stabilizer. 6-methyl-1,3,3a, 7-tetrazaindene, a dispersion of polyethyl acrylate, an aqueous latex (a) represented by the following structural formula, polyethylene glycol, 1,3-divinylsulfonyl-2-propanol and Compound C below, and a book Compound C After adding the compound of the general formula (I) of the invention as shown in Table 3, the amount of silver on the polyethylene terephthalate film was 3.4 g.
The coating was performed at a rate of / m ² to prepare Samples 1 to 11. Similarly, a sample containing the comparative compounds (a) and (b) (1
2) to (15) were prepared. Exposing and developing each sample,
Photographic properties as a photosensitive material for plate making were evaluated.

The relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of 1.5 at 38 ° C. for 30 seconds development, and the value of Sample 1 is set to 100.

○ Black spots are evaluated on a scale of 5 by microscopic observation. “5” is the best and “1” is the worst quality.
"5" or "4" is practical, "3" is poor but practically usable, and "2" or "1" is not practical. "3"
The one between "4" and "4" was evaluated as "3.5", and the one between "4" and "5" was evaluated as "4.5".

○ The evaluation of black spots is the result of development at 38 ° C for 40 seconds.

The compounds used in Example 2 were used as the comparative compounds (a) and (b), and the following compounds were used.

The results are shown in Table 3 as Photographic Properties-1. For the development, a developer having the following formulation was used.

Developer Hydroquinone 45.0g N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 18.0g Potassium hydroxide 55.0g 5-Sulfosalicylic acid 45.0g Boric acid 25.0g Potassium sulfite 110.0g Ethylenediaminetetraacetic acid disodium salt 1.0g Potassium bromide 6.0g 5-Methylbenzotriazole 0.6g n-Butyl-diethanolamine 15.0g Water was added 1 (pH = 11.6) Also, each untreated sample was treated at 50 ° C and 75% relative humidity. After standing for 3 days, the photographic properties were similarly determined and shown in Table 3 as photographic property-2.

As is clear from Table 3, Samples 1 and 2 which do not use the compound of the general formula (I) show good sensitivity and gradation, but have poor black spot characteristics. Even if the emulsion was changed from I to II and the sensitivity was changed, the black spot was not greatly improved.

Comparative samples (12) to (1) in which the compound of the general formula (I) is used in combination.
In 5), the black spots are good, but the sensitivity is low and the tone becomes soft. (1
6) to (21) have good sensitivity and gradation, but the emission speed is slow and black spots are poor. On the other hand, in (22) to (24), the comparative compound e is extremely unstable, and the sensitivity and γ are remarkably lowered, especially in the forced deterioration test (photographic characteristic 2).

On the other hand, sample 5 obtained by treating the compound represented by the general formula (I) in the presence of dihydroxybenzene as in the present invention.
Nos. 11 to 11 showed good black spot characteristics, and also showed good sensitivity and gradation even after the forced deterioration test.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one blocked photographic reagent represented by the general formula (I) which releases a development inhibitor and a hydrazine derivative is imagewise exposed to dihydroxybenzenes and / or Alternatively, the image forming method is characterized by processing in the presence of aminohydroxybenzenes. General formula (I) (In the formula, X ¹ is C via a nitrogen atom or an oxygen atom of the linking group.
Represents a divalent linking group bonded to PUG, and PUG represents a development inhibitor bonded to X ¹ via a heteroatom of PUG,
R ¹ , R ² and R ³ represent a hydrogen atom or a substitutable group, R ¹
And R ² and R ¹ and R ³ may combine with each other to form a carbocycle or a heterocycle. A cyano group or a nitro group (wherein R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom or a substitutable group), and n and m represent 0 or 1. However, when m = 0, the development inhibitor represented by PUG binds to C at the nitrogen atom or oxygen atom of PUG. )