JPS62245263A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of releasing a photographic useful reagent with a prescribed timing at the time of processing, and of producing easily and inexpensibly, preventing the desensitizing and the generation of fog by incorporating one kind of specific photographic reagent to the titled material. CONSTITUTION:At least one kind of the photographic reagents shown by the formula is incorporated to the titled material having at least one layer of the photosensitive silver halide emulsion layer. In the R<1> and R<2> are each hydrogen atom or alkyl group, etc., R<3> and R<4> are each cycloalkyl group, etc., R<5> is hydrogen atom or acyl group, X is oxygen atom, etc., (time) is a timing group, (t) is 0 or 1, PUG is a photographic useful group. The preferable used amount of a photographic reagent shown by the formula is 10<-8>-10<-1>mol of an anti- fogging agent and a development stopping agent per 1mol of silver.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Technical Field The present invention relates to silver halide photographic materials comprising a light-sensitive silver halide emulsion layer in which blocked photographic reagents are combined that release photographically useful reagents.

Prior art and its problems By adding a photographically useful photographic reagent to the photographic light-sensitive material in advance and exerting its effect, it has different characteristics from when the photographic reagent is contained in the processing solution. can be achieved.

Its characteristics include acid, alkali, oxidation,
It is possible to effectively utilize photographic reagents that easily decompose under reducing conditions and cannot withstand long-term storage in processing facilities, 2) The composition of the processing solution is simplified and preparation is easy, and 3) It is necessary at the necessary timing during processing. 4) It is possible to apply the necessary photographic reagent only to the necessary location, that is, a certain layer of the multilayer photosensitive material and/or layers in its vicinity; The ability to vary the working amount of photographic reagents as a function of silveride development, etc. However, if a photographic reagent is added to a photographic material in an active form, it may react with other components in the photographic material or decompose due to the influence of heat, oxygen, etc. during storage prior to processing. As a result, the expected performance cannot be achieved during processing.

One method to solve this interlayer problem is to block the active groups of photographic reagents and add them to photographic materials in a form that is substantially inactive in the photographic material, that is, as a photographic reagent precursor, which is then added to the photographic material in the form of a photographic reagent precursor. Sometimes there is a way to generate photographic reagents for the first time.

According to this method, when a useful photographic reagent is, for example, a dye, the desired spectral absorption can be obtained by blocking the functional groups that greatly affect the spectral absorption of the dye and shifting the spectral absorption toward shorter or longer wavelengths. Even if it is coexisting in the same layer as a silver halide emulsion layer having a sensitive spectral region, it has the advantage that sensitivity does not decrease due to the so-called filter effect. In addition, if the useful photographic reagent is an antifoggant or a development inhibitor, by blocking the active groups, it is possible to suppress the desensitizing effect due to adsorption to photosensitive silver halide during storage and formation of silver salts. By releasing these photographic reagents at the necessary timing during the development process,
This method has advantages such as reducing fog without impairing sensitivity, suppressing overdevelopment fog, and being able to stop development at a required time.

When useful photographic reagents are developing agents, auxiliary developers, development accelerators, or nucleating agents, blocking the active or adsorbing groups can prevent various photographic effects due to the formation of semiquinones and oxidants during storage. There are advantages such as preventing generation of fog nuclei during storage by preventing adverse effects or electron injection into silver halide, and as a result, stable processing can be realized. Photographic reagents may be bleach accelerators or
In the case of fixation accelerators, by blocking their active groups, they suppress reactions with other coexisting components during storage.
One advantage is that by removing the protecting group during treatment, the desired performance can be exhibited at the required time.

As mentioned above, the use of precursors for photographic reagents can be an extremely effective means for fully demonstrating the performance of photographic reagents. However, on the other hand, these precursors must satisfy extremely strict conflicting requirements. Must. In other words, it must balance the contradictory requirements of being stable under storage conditions and releasing the blocking group at the required timing during processing to release the photographic reagent quickly and efficiently. -No.

Several blocking techniques for photographic reagents are already known. For example, those using blocking groups such as acyl groups and sulfonyl groups described in Japanese Patent Publication No. 47-4480-5, Japanese Patent Publication Nos. 54-39727 and 5
Nos. 5-9696 and 55-34927, which utilize a blocking group that releases a photographic reagent through the so-called reverse Michael reaction; JP-A No. 57-136640, which utilizes a blocking group that releases a photographic reagent with the production of quinone methide or a quinone methide-like compound through intramolecular electron transfer; or JP-A-57-76541
Known techniques include those that utilize 5- or 6-member cleavage as described in Japanese Patent No. 57-135949 and Japanese Patent No. 57-179842.

Furthermore, a method is known in which a compound that promotes the cleavage of a photographic reagent precursor is added to a processing solution or a photographic light-sensitive material to accelerate the release of a photographic reagent during processing. A combination of hydroxylamines and a ring-cleavage type precursor described in JP-A-59-198453, a combination of hydroxamic acids and a ring-cleavage-type precursor described in JP-A-59-198453, and JP-A-60-35729 A combination of the described oximes and a ring-cleavage precursor, JP-A-59-2184
Examples include a combination of sulfites and a levulinic acid type precursor described in Japanese Patent Publication No. 39, and a combination of sulfites and an α,β-unsaturated carbonyl type precursor described in JP-A-59-201057.

However, in the conventional blocking technology of photographic reagents, the release rate of photographic reagents that are stable under storage conditions is too slow during processing, requiring high alkaline treatment at pH 13 or higher, or treatment at pH 9 to 12. Even if the release rate is sufficient in liquid form, it has the disadvantage that it gradually decomposes under storage conditions, impairing its function as a 0% precursor. Further, even in combination with an accelerator, the accelerating effect is still insufficient.

■Object of the invention The object of the present invention is to be completely stable under storage conditions, to be able to release photographically useful reagents at a desired timing during development processing, and to be particularly suitable for processing solutions with a relatively low pi of pH 9 to 12. To provide a silver halide photographic light-sensitive material containing a photographic reagent that can release a photographically useful reagent in a timely manner, prevent desensitization and fogging, and can be easily synthesized at low cost even when processed with be.

■Disclosure of invention Such objects are achieved by the invention described below.

That is, the present invention provides a silver halide photographic material having at least one light-sensitive silver halide emulsion layer,
This is a silver halide photographic light-sensitive material characterized by containing at least one photographic reagent represented by the following general formula (I).

General formula (I) (In the above general formula (I), R1 and R2 are each a hydrogen atom, or a substituted or I#-substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, or heterocycle Represents a residue.

R3 and R4 are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic residue, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl group Represents a sulfonyl group, arylsulfonyl group, alkylphosphoryl group, arylphosphoryl group or sulfamoyl group.

R5 represents a hydrogen atom, or a substituted or unsubstituted acyl group, alkoxycarbonyl group or aryloxycanrebonyl group. Also, R1 and R2, R1 and R
3, and R3 and R4 may be connected to each other to form a saturated or unsaturated ring, if possible. X represents an oxygen atom, a sulfur atom, or an imino group. (Li■C) represents a timing group, and t represents 0 or 1.

PUG represents a halogen atom (in this case t=0) or a photographically useful group. )■ Specific configuration of the invention The specific configuration of the present invention will be explained in detail below.

The silver halide photographic light-sensitive material of the present invention has at least one light-sensitive silver halide emulsion layer, and has the following general formula (I).
Contains at least one photographic reagent represented by:

General Formula (I) In the above general formula (I), R1 and R2 are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (for example, a methyl group, an ethyl group, an isopropyl group,
Allyl group, hexyl group, 2-decyl group, t-octyl group, octadecyl group, trifluoromethyl group, 3-phenoxypropyl group, etc.): Substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms (e.g. cyclopentyl group) , cyclohexyl group, etc.)
: Substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms (
For example, vinyl group, styryl group, propenyl group, etc.): Substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms (
For example, ethynyl group, propynyl group, phenylethynyl group): Substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms (
(e.g., benzyl group, 2-phenylethyl group, etc.); Substituted or unsubstituted aryl group having 6 to 20 carbon atoms (e.g., phenyl group, 4-chlorophenyl group, 4-methoxyphenyl group, naphthyl group, etc.): 1 to 20 carbon atoms It represents 20 substituted or unsubstituted heterocyclic residues (eg, 2-pyridyl group, 2-furfuryl group, benzoxazol-2-yl group, etc.).

R3 and R4 are all substituents other than the hydrogen atoms mentioned in R1 and R2: substituted or unsubstituted acyl groups having 2 to 25 carbon atoms (e.g. acetyl group, propanoyl group, hexanoyl group, pivaloyl group, dodecanoyl group) , octadecanoyl group, benzoyl group, acryloyl group, propioloyl group, etc.); C2-C25 substituted or unsubstituted alkoxycarbonyl group (e.g. methoxycarbonyl group, n-butoxycarbonyl group, dodecyloxycarbonyl group, octadecyloxy carbonyl group, etc.): /# table divisor 6~25'M φ117 (gate) Aryloxycarbonyl group of L2 island (e.g. phenoxycarbonyl group, naphthyloxycarbonyl group, furfuryl-2-oxycarbonyl group, 3-pentadecyl group) (oxycarbonyl group, etc.): Substituted or unsubstituted carbamoyl group having 1 to 25 carbon atoms (e.g., ethylaminocarbonyl group, dibutylaminocarbonyl group, dodecyloxyethylaminocarbonyl group, dodecylmethylaminocarbonyl group, 2
．． (4-di-t-acylphenoxypropylaminocarbonyl group, phenylcarbamoyl group, etc.); Substituted or unsubstituted alkylsulfonyl group or arylsulfonyl group having 1 to 25 carbon atoms (for example, methanesulfonyl group, octylsulfonyl group, benzenesulfonyl group) (p-toluenesulfonyl group, etc.); Substituted or unsubstituted alkylphosphoryl group or arylphosphoryl group having 1 to 25 carbon atoms (e.g. dimethylphosphoryl group, diphenylphosphoryl group, etc.); Substituted or unsubstituted group having 0 to 25 carbon atoms represents a sulfamoyl group (eg, sulfamoyl group, ethylsulfamoyl group, dipropylsulfamoyl group, dodecyloxyethylsulfamoyl group, ethyl-dodecylsulfamoyl group, etc.).

R5 is a hydrogen atom; a substituted or unsubstituted acyl group having 2 to 25 carbon atoms (e.g. acetyl group, hexanoyl group, trifluoroacetyl group, benzoyl group, p-chlorobenzoyl group, etc.); a substituted or unsubstituted acyl group having 2 to z5 carbon atoms; unsubstituted alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group,
dodecyloxycarbonyl group, etc.): Substituted or unsubstituted aryloxycarbonyl group having 6 to 25 carbon atoms (e.g. phenoxycarbonyl group, naphthyloxycarbonyl group, pyridyl-2-oxycarbonyl group, 3-pentadecyloxyphenoxycarbonyl group, 4 -chlorophenoxycarbonyl group, etc.).

In addition, R1 and R2, R1 and R3, and R3 and R4 are connected to each other when possible, and are saturated or unsaturated rings (for example, cyclohexane ring when RI and R2, Ht and R3 When R3 and R4, an indolizinone ring, etc.) may be formed.

Preferably, as a substituent for R1 to R5,
Alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, aralkyl group, acylamino group, amino group, halogen atom, acyloxy group, hydroxyl group, carboxyl group, cyano group, acyl group, carbamoyl group group, sulfamoyl group,
Sulfamoylamino group, ureido group, sulfonyl group,
Examples include sulfonylamino group, nitro group, alkylthio group, arylthio group, sulfinyl group, and heterocyclic group.

X represents an oxygen atom, a sulfur atom or an imino group.

(ti■e) represents a timing group, t is 0 or l
represents. PUG represents a halogen atom (1=0 in this case) or a photographically useful group.

Next, (ti■C) and PUG will be explained in detail.

The timing group represented by (ti■e) is known per se, and has the function of temporally shifting (timing) the state in which the residue represented by PUG is formed. In other words, the bond is cleaved ゛(-Li■e
-)-After the PUG residue is generated, PUG and (ti■e)
(Li+*e) has the function of requiring a certain amount of time for the bond between it to cleave. Therefore (-L
If the i5e+PUG has diffusivity, it is possible to design a PUG that is generated at a location distant from the point where the precursor of the present invention is incorporated.

As for the timing base expressed by (Li■e), a child has the following timing:
-145135) etc., a photographically useful group (the above-mentioned P'
UG): U.S. Patent No. 4,310.6i2
No. (JP-A-55-53330) and No. 4,358,
No. 525, etc., which releases PUG through an intramolecular ring-closing reaction after ring opening: U.S. Patent No. 4,330.617
4,446,216, 4,483,919°, JP-A-59-121328, etc., ifi hydrate obtained by intramolecular ring-closing reaction of the carboxyl group of succinic acid monoester or its analogs. U.S. Pat. No. 4,409,323, U.S. Pat.
No. 421,845, Research Disclosure Magazine
No. 21228 (December 1981), U.S. Patent No. 4
, No. 416,977 (Japanese Unexamined Patent Publication No. 57-135944),
Kinozentsumethane or its analogs are produced by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group as described in JP-A-58-209736, JP-A-58-209738, etc. What releases PUG: U.S. Patent No. 4,420,554
6640), JP-A-57-135945, JP-A-57-135945
No. 188035, No. 5B-98728 and No. 58-
P from the γ-position of the enamine by electron transfer of the enamine structure-containing part of the needle ring to the nitrogen-containing structure described in No. 209737, etc.
Those that release UG: Those that release PUG through an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with the nitrogen atom of a nitrogen-containing heterocycle described in JP-A No. 57-56837. U.S. Patent No. 4.146.3
No. 96 (JP-A No. 52-90932), JP-A No. 59-9
3442, JP-A-59-75475, etc., which release PUG with the production of aldehydes; JP-A-51-146828, JP-A-57-179842, JP-A-5
9-104641 which releases PUG with decarboxylation of the carboxyl group; has the structure -0-COOCRIR12-PUG and releases PUG with decarboxylation and subsequent generation of aldehydes. What to do; Japanese Patent Publication No. 6
No. 0-7429 which releases PUG with formation of isoyanate; U.S. Pat. No. 4,438,193
Examples include those that release PUG through a coupling reaction with an oxidized product of a color developer described in No. 1, etc.

As the group represented by (Li-〇), the following general formula (T
-1) to (T-10) are preferred.
Here (ri represents the part that binds to the dashed line side, (*)
(*) represents the site where PUG binds.

General formula (T-1) (R -0-CH2-0-1(*)-0-CH2-■ (*)-0-CH2-3-1<*>-C-C-
6 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

xl is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -
〇-Rfu, -SRfu, -QC-R7, -C
O-R7, -5O2-R7, cyano group, halogen atom (
For example, it represents a fluorine, chlorine, bromine, iodine) or a nitro group. Here, R7 and RJI may be the same or different and represent a group having the same meaning as R6. X
2 represents the group described for R6.

9 represents an integer from 1 to 4. xl when 9 is 2 or more
The substituents represented by may be the same or different.
When q is 2 or more, xl may be connected to each other to form a ring.

n represents 0.1 or 2.

The group represented by general formula (T-1) is, for example, US Pat.
, No. 248,962.

General formula (T-2) In the formula, regarding zl, xi, x2, and q, the general formula (
It has the same meaning as defined in T-1).

General formula (T-3) 22 in the formula represents (ne)-〇-1(*)-O-C-1.

m is an integer from 1 to 4, preferably 1.2 or 3.

R6 and x2 have the same meaning as defined in general formula (T-1).

General formula (T-4) In the formula, 23 is (*) Represents -0-CH2-S-.

R6, R7, Ra, X8 and q& have the same meaning as defined in general formula (Ti).

The group represented by general formula (T-4) is, for example, described in U.S. Pat.
, 409, 323.

General formula (T-5) In the formula, 23, R7, R', Xl and qld general formula (T
It has the same meaning as defined in -4).

General formula (T-6) In the formula, x3 is selected from carbon, nitrogen, oxygen, or sulfur, consists of a combination of at least one atom, and is an atom necessary to form a three-membered or supra-heterocyclic ring. It is a group. This heterocycle may further be fused with a benzene ring or a three-membered or supra-membered heterocycle. Preferred heterocycles include, for example, virole, pyrazole, imidazole, triazole, furan, oxazole, thiophene, thiazole, pyridine, ridazine, pyrimidine, pyrazine, azepine, oxepine, indole, benzofuran and quinoline.

Q3. Xt, q, R represent the same meaning as defined in general formula (T-4). General formula (T-6)
For example, the group represented by British Patent No. 2,096,783
This is the timing group described in No.

General formula (T-7) In the formula, x5 consists of a combination of at least one atom selected from carbon, nitrogen, oxygen, or sulfur, and is an atom necessary to form a three-membered or supraheterocyclic ring. It is a group. x8 and x7 represent a hydrogen atom, an aliphatic group or an aromatic group. This heterocycle may further be fused with a benzene ring or a three-membered or supra-membered heterocycle.

Preferred heterocycles include virol, imidazole, triazolefuran, oxazole, oxadiazole,
Thiophene, thiazole, thiadiazole, pyridine,
Examples include pyridazine, pyrimidine, pyrazine, azepine, oxepine and isoquinoline.

Q3, Xt, and q have the same meanings as defined a in formula 111 (T-4).

General formula (T-8) In 2 In the formula, X In consists of a combination of at least one or more atoms selected from carbon, nitrogen, oxygen or sulfur to form a three-membered or supra-heterocyclic ring. It is a necessary atomic group. The XaJ and x9 rings may be further fused with a benzene ring or a three-membered or supra-membered heterocycle.

Ql,X! ,X2. n, q&, general formula (T-1)
It has the same meaning as defined in .

General formula (T-9)
expresses the same meaning as Q3 represents the same meaning as defined in general formula (T-4).

L represents 0 or 1.

Preferred heterocycles are, for example, those shown below.

represents an aliphatic group, an aromatic group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a heterocyclic group, or a carbamoyl group.

General formula (T-10) In the formula, Xi, x2, B, General formula (T-1) Te, and Z3 represent the same meanings as defined in the general formula (T-4).
m has the same meaning as defined in general formula (T-3), and is preferably 1 or 2.

From the above general formula (T-1) to (T-10), xl
,X2. When R8, R7, R♂ and R9 contain an aliphatic group moiety, it preferably has 1 to 20 carbon atoms, and is saturated or unsaturated, substituted or unsubstituted, chain or cyclic, straight chain or branched. It's okay. Above x1,
When 2, R8, Rf, R8k, l- and R9 contain an aromatic group moiety, they have 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and are more preferably substituted or unsubstituted phenyl groups. In addition, when x1, It is.

Preferred examples of the hetero I12 group include a pyridyl group, a furyl group, a chenyl group, a triazolyl group, an imidazolyl group, a pyrazolyl group, a thiadiazolyl group, an oxadiazolyl group, and a pyrrolidinyl group.

Preferred examples of timing groups include those shown below.

(lO) し2r15 t,, n3 (le) (19)(°( (°( (°( (°( (°( (30) (:
11)%+, n3 (3:l) (:14)(
4υ PUG is a halogen atom or +tiIIe+P UG
Alternatively, it represents a photographically useful group as PUG.

Photographically useful groups include, for example, development inhibitors, development accelerators, nucleating agents, couplers, diffusible or non-diffusible dyes, desilvering accelerators, silver dispersing inhibitors, silver halide solvents, Compounds, developing agents, auxiliary developing agents, fixing accelerators, fixing inhibitors, image stabilizers, toning agents, processing dependency improvers, halftone dot improvers, color image stabilizers, photographic dyes, surfactants agent, hardening agent,
Represents a desensitizer, contrast agent, chelating agent, optical brightener, etc., or a precursor thereof.

Since these photographically useful groups often overlap in terms of usefulness, representative examples will be specifically explained below.

Examples of development inhibitors include compounds having a mercapto group bonded to a heterocycle, such as substituted or unsubstituted mercaptoazoles (specifically 1-phenyl-5-mercaptotetrazole, 1-(4-carboxyphenyl)). −
5-mercaptotetrazole, 1-(3-and droxyphenyl)-5-mercaptotetrazole, 1-(4-sulfophenyl)-5-mercaptotetrazole, 1-(
3-sulfophenyl)-5-mercaptotetrazole,
1-(4-sulf1moylphenyl)-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, l-te4-n-hex, dylcarbamoyl, °, “phenyl)-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.), substituted or unsubstituted mercaptoazaindenes (specifically, 6
-Methyl-4-mercapto-1,3,3a, 7-tetrazaindene, 6-methyl-2-benzyl-4-mercapto-1,3,3a, futetrazaindene, 6-phenyl, -4-mercapto tetrazaindene, 4.6-dimethyl-2-mercapto-1゜3.3a, 7-tetrazaindene, etc.), substituted or unsubstituted mercaptopyrimidines (specifically 2-mercaptopyrimidine, 2-
mercapto-4-methyl-6-hydroxypyrimidine, 2-mercapto-4-propylpyrimidine, etc.). Petrocyclic compounds capable of producing iminosilver, such as 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 (in particular,
5-nitrobenzimidazole, 4-nitrobenzimidazole, 5.6-dichlorobenzimidazole, 5-
cyano-6-chlorobenzimidazole, 5-trifluoromethyl-6-chloropenzimidazole, etc.). In addition, the development inhibitor becomes a compound having development inhibitory properties after being released from the mother nucleus of general formula (I) in the development treatment process, and furthermore, it becomes a compound that has development inhibitory properties or is significantly reduced. It may also be a compound that changes into a chemical compound.

in particular! -(3-phenoxycarbonylphenyl)
-5-mercaptotetrazole, 1-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole,
! -(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-(butoxycarbonyl) methoxycarbonyl)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-mercabuto-1,3,4-thiadiazole, 5-cinnamoylaminobenzotriazole, '1-(3-vinylcarbonyl) phenyl)-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-)lyazole,6-phenoxycarbonyl-
Examples include 2-mercaptobenzoxazole.

When PUG is a diffusible or non-diffusible dye, specific examples of preferable dyes as dye precursors whose absorption wavelengths have been temporarily shifted are shown below.

Examples of the case where PUG is a silver halide solvent include JP-A-60-163042 and U.S. Pat. No. 4,003,9.
10, U.S. Patent No. 4,378.424, etc., mercaptoazoles or azolethiones having an amino group as a substituent described in JP-A-57-202531, etc. More specifically, those described in Japanese Patent Application No. 71768/1980 can be mentioned.

An example of the case where PIG is a nucleating agent is JP-A-59-1
Examples include the part of the leaving group released from the couplers described in No. 70840.

Regarding other PUGs, the descriptions in Japanese Patent Application No. 71768/1982, US Pat. No. 4,248,962, etc. can be referred to.

Specific examples of the compounds of the present invention are listed below, but the present invention is not limited thereto.

NnLL;5 tltl Shiku J2 N! 6 4! The release of PUG from the blocked photographic reagent represented by general formula (I) of the present invention is estimated as follows (Scheme 1).

Scheme 1 (Shows the case where t=0, R5=H) (V) (However, R1%R4, X and PUG are synonymous with those shown in general formula (I).) In Scheme 1, (I) From (n), (m) and (r
In the reaction producing V), PUG is a chlorine atom, R1, R4
When is a hydrogen atom and X is an oxygen atom, W, J,
It has been discussed in detail by le Noble et al.
ahedron Letters, Vol, 22.41
7 (1981), the results are reported.

However, there is no study of atoms other than chlorine atoms.

Therefore, it is unclear whether the compound represented by the general formula (I) that we have investigated actually decomposes by the reaction mechanism proposed by W, J, Ie Noble, etc. Furthermore, it is unclear whether the decomposition reaction of (■) also proceeds in the same way. It is.

However, we found that the rate of separation of PUG in Scheme 1 can be greatly changed depending on all the substituents including PUG, so it is important to select appropriate substituents according to the various uses and purposes of the photographic material. This allows the performance to be fully demonstrated.

One of the characteristics of the present invention is that the compound represented by the general formula (I) is extremely easy to synthesize. The starting material is a carboxylic acid or its ester (IV) substituted with a halogen atom (X-) at the α-position, which can be produced at low cost as a synthetic intermediate for couplers, and the degree of reactivity of Ze, which is a photographically useful group, is The order of synthesis of the connection (route a) and the conversion to hydrazide (route b) is determined according to . The compound of the present invention is characterized by being easily decomposed under basic conditions, but in order to obtain the highly active synthetic intermediate (I), the reaction with basic hydrazines can also be carried out in acetic acid. achieved.

In order to explain the contents of the present invention more clearly, typical synthesis examples are shown below.

(III) Synthesis of Ju11 N,N-dimethyl-N'-(1-phenyltetrazolyl-2-thio)acetohydrazide (Exemplary Compound 1) t-i, 2-methoxycarbonylmethyl-1-phenyltetrazole Methyl 10 mJl of bromoacetate to 3 ml of acetonitrile
After adding 17.8 g of 2-mercapto-1-phenyltetrazole, 8.1 d of pyridine was gradually added. After stirring for 30 minutes, the reaction mixture was poured into 300-m water.

The white crystals produced were filtered under reduced pressure and washed with water.

Yield 24.6g Yield 98% 1-2. Synthesis of Exemplified Compound 1 N,N-dimethylhydrazine 10- and dimethylformamide! A mixture of 4 g of compound (1-1) and 10-dimethylformamide was gradually added to the mixture of 0- and 10-dimethylformamide. After 3 hours, the reaction mixture was poured into 100-g water, and the resulting white crystals were filtered under reduced pressure and washed with water. This was recrystallized from isopropanol.

Yield: 3.9 g Yield: 88% Mp, 131-2°C
1-phenyltetrazolyl-2-thio)) pentanecarbohydrazide (Exemplary compound 2-1. Synthesis of 2-bromohexanoyl chloride 155 g of 2-bromohexanoic acid, 150 g of thionyl chloride
The mixture was heated to reflux in an oil bath for 4 hours. After removing excess thionyl chloride under reduced pressure, subsequent vacuum distillation was performed to obtain a colorless liquid.

Yield 142.4g Yield 84% bp, 95℃730
-mHg 2-2. N-phenyl-N'-(1-(1-phenyltetrazolyl-2-thio)) Synthesis of pentane carbohydrazide Mix 2.7-phenylhydrazine, 2.5 ml of pyridine, and 50-ml of acetonitrile, and cool on ice. Cooled to -10°C in a methanol bath. Compound (2-1) 411!
and acetonitrile lO- was added over 30 minutes at -5°C or below. After further stirring for 2 hours under water cooling, 5 g of 2-mercapto-1-phenyltetrazole and then 2.5 g of pyridine were gradually added. The water bath was removed, and after 2 hours it was poured into water and extracted with ethyl acetate. This was dried with Glauber's salt and purified by silica chromatography.

Yield: 6.8 g Yield: 59% Mp, 127-8°C 1-31 Synthesis of Exemplary Compound 14 25 g of compound (2-2) was dissolved in a mixture of 100 ml of acetonitrile and 100 d of dimethylformamide, and methanesulfonyl chloride 13iIQ was added. Thereafter, pyridine 1O- was gradually added and left overnight.

This was poured into 12 water, and the obtained crystals were filtered under reduced pressure, washed with water, and recrystallized from isopropanol.

Yield: 21 g Yield: 70% Mp, 115-6°C The preferred amount of the photographic reagent of the present invention represented by the general formula (I) varies depending on the type of photographically useful reagent to be released, but the amount of antifogging per mole of silver is The market agent and development stopper are 104
~10-1 mol, preferably 10'-10-1 mol for mercapto antifoggants, 10-5-10-1 mol for azole antifoggants such as benzotriazole, and silver for black and white developers such as hydroquinones. 10-t per mole
10 moles, preferably 0.1 to 5 moles, pyrazolidone co-developers from 10-4 to 10 moles, preferably 10-2 to 5 moles per mole of silver, and development accelerators or nucleating agents per mole of silver. 10-! ~10-6 mol, preferably 1
0-3 to 10-5 mol, silver halide solvents such as sodium thiosulfate, 101 to 10 mol, preferably lO-2 to 1 mol, dyes or color materials for color diffusion transfer photography per mol of silver. 1 O-3 to 1 mol, preferably 5×1 O to 0.5 mol.

The blocked photographic reagent (precursor) represented by the general formula (I) of the present invention includes a silver halide emulsion layer, a coloring material layer, an undercoat layer, a protective layer, an intermediate layer, a filter layer, It may be added to any of the antihalation layers, image-receiving layers or cover sheet layers for monochrome or color diffusion transfer methods, and other auxiliary layers.

In order to add the precursor used in the present invention to these layers, the precursor can be added to the coating solution for layer formation either as is or in a solvent that does not have an adverse effect on the photographic material, such as water or alcohol. It can be added after being dissolved at an appropriate concentration. Alternatively, the precursor can be dissolved in a high boiling point organic solvent and/or a low boiling point solvent,
It can also be added after being emulsified and dispersed in an aqueous solution. Alternatively, it may be added by impregnating it into a polymer latex by the method described in JP-A Nos. 51-39853, 51-59942, 54-32552, and US Pat. No. 4,199.363.

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

The compounds of the present invention can be used, for example, in coupler-type color photographic materials.

A general method for forming color images from color photographic materials is the subtractive color method, in which silver halide emulsions are selectively sensitive to blue, green, and red, and yellow, magenta, and cyan, which are redundant colors, are selectively exposed to blue, green, and red. color image forming agents are used. To form a yellow image, for example, acylacetanilide or dibenzoylmethane couplers are used, and to form a magenta image, pyrazolone, pyrazolobenzimidazole,
Cyanoacetophenone or indacylon couplers are used, and primarily phenolic couplers such as phenols and naphthols are used to form cyan images.

Normally, color photographic materials are roughly divided into two types: an external method in which couplers are placed in a developing solution, and an internal method in which couplers are incorporated in each photosensitive layer of the material so as to maintain their independent functions. Ru. In the latter, the dye image-forming coupler is added to the silver halide emulsion.

The coupler added to the emulsion must be non-diffusible (diffusible) in the emulsion binder matrix.

In the internal mold method, the processing process for color photographic materials consists of the following three processes.

(1) Color development process (2) 1 separate process (3) Fixing process Bleaching process and fixing process can also be performed at the same time.
That is, it is a bleach-fixing process (so-called Brix), which desilveres developed silver and undeveloped silver halide. In addition to the two JJ and basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary processes such as maintaining the photographic and physical quality of the image or improving the storage stability of the image. It involves a process. for example,
A hardening bath to prevent excessive softening of the photosensitive film during processing, a stop bath to effectively stop the development reaction, an image stabilization bath to stabilize the image, and a defilming bath to remove the backing layer of the support. Examples include processes such as:

In order to introduce a coupler into the silver halide photographic material of the present invention, conventionally known methods include adding or dispersing the coupler to an emulsion, and adding the coupler to a gelatin/silver halide emulsion or a hydrophilic colloid. applies. For example, a method of mixing and dispersing a coupler with a high boiling point organic solvent such as dibutyl phthalate, tricresyl phosphate, wax, higher fatty acids and their esters, etc., for example, U.S. Pat. Nos. 2,304,939 and 2,322,027 issue,
The method described in U.S. Pat. , No. 170, No. 2,801,
171, No. 2,949°360, etc., the coupler itself has a sufficiently low melting point (e.g. 75°C
(below), a method of dispersing it alone or in combination with other couplers such as colored couplers or uncolored couplers, such as German Patent No. 1,
143.707 etc. apply.

Dispersion aids include commonly used anionic surfactants (e.g. sodium alkylbenzene sulfonate,
Sodium di-octyl sulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate, Fischer type couplers, etc.), amphoteric surfactants (such as N-tetradecyl/N-N dipolyethylene alpha betaine, etc.) and nonionic surfactants. agents such as sorbitan, monolaurate, etc. are used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color-forming coupler that forms color through oxidative coupling with an aromatic primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative) during color development processing. It may also contain a vine compound. For example, magenta couplers include 5-pyrazolone couplers, pyrazolopenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (
Examples of the cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). Also D
In addition to IR couplers, the products of the coupling reaction may include colorless DLR coupling compounds that are colorless and release development inhibitors.

When applying the photographic elements of this invention to color diffusion transfer photography, peeling Il! (Beer Apart) type or JP-B No. 46-16356, JP-A No. 48-33697, JP-A-5
No. 0-13040 and British Patent No. 1,330.524
Integrated as described in the issue.
It is possible to adopt a structure of a film unit that does not require mowing as described in Japanese Patent Application Laid-open No. 57-119345.

The compounds of the present invention can also be used in black-and-white photographic materials. X- for direct medical use as a black and white photosensitive material
Examples include ray film, black and white film for general photography, lithographic film, and scanner film.

Other configurations of the silver halide photographic material of the present invention, such as a method for producing a silver halide emulsion, a halogen composition,
Crystal habit, particle size, chemical sensitizer, antifoggant, stabilizer, surfactant, gelatin hardener, hydrophilic colloid binder, matting agent, dye, sensitizing dye, antifading agent, color mixing inhibitor, polymer Latex 1. Brightener, antistatic agent,
There are no particular restrictions on such matters; for example, research disclosure
re) Volume 176, pages 22-31 (December 1978) can be referred to.

The compound of the present invention is also suitable for activator treatment in which a color developing agent or its precursor is incorporated into a light-sensitive material and treated in an alkaline bath. Furthermore, when the activator treatment is performed at a high temperature of 50° C. or higher, it is possible to select a precursor that is advantageous in terms of storage stability, and the compounds of the present invention can also be used for such purposes.

Further, a method for exposing the silver halide photographic material of the present invention,
There are no particular restrictions on the developing method, and any of the known methods and known processing solutions, such as those described on pages 28 to 30 of the above-mentioned Research Disclosure, can be applied. This photographic processing may be either a photographic processing for forming a silver image (black and white photographic processing) or a photographic processing for forming a dye image (color photographic processing), depending on the purpose. Processing temperature is usually 18℃ to 5
selected between 0°C but below 18°C or 50°C
The temperature may exceed ℃. In particular, when used in high-temperature processing or heat-developable photosensitive materials that are processed at temperatures above 50°C, the protection reaction of the precursor is accelerated and the rate of release of photographically useful reagents is increased, so selection of a precursor is advantageous in terms of storage stability. becomes possible.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (for example, hydroquinone),
3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. can be used alone or in combination. The developing solution generally contains other known preservatives, alkaline agents, pHM street agents, antifoggants, etc., as well as solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc., as necessary. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like.

The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" development processing is a process in which dihydroxybenzenes are usually used as a developing agent and development is performed at a low bisulfate ion concentration for the photographic reproduction of line images or the halftone dot photographic reproduction of halftone images. It refers to a developing process that causes the process to be carried out contagiously.

Also, U.S. Patent Nos. 4,166.742 and 4.168,
No. 977, No. 4,221,857, No. 4,224,4
No. 01, No. 4,243゜739, No. 4,272,60
When the method of the present invention is applied to the method of developing a surface latent image type emulsion in the presence of a hydrazine compound to obtain high-contrast photographic characteristics as described in No. 6 and No. 4,311.781, halftone images and It is effective in reproducing line drawings, and it is possible to obtain photographic characteristics with extremely high sensitivity and high contrast, and with less occurrence of non-imagewise fine dot-like blackening phenomenon called black spots.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known general aromatic amine developer, such as 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-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, "Photo Processing Chemistry" by F. A. Mason (published by Focal Press) [L. F. 8. Mason.

1'hoLographic Processing
[:hcmisLry(Foca11'ress)]
, 19966, pp. 226-229, U.S. Patent No. 2,1
No. 93,015, No. 2.592.364, JP-A No. 4
Those described in No. 8-64933 may be used.

The compound of the present invention can also be used in heat-developable photosensitive materials as described above.

The structure, processing method, etc. of the photothermographic material of the present invention will be explained below.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Alternatively, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide may be used.

Specifically, U.S. Patent No. 4,500,626, column 50, Research Disclosure, June 1987 issue 9.
Pages - lO pages (RD17029), Tokugansho, 59-228
No. 551, No. 60-225176, No. 60-2282
Any of the silver halide emulsions described in No. 67 and the like can be used.

The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Further, in the present invention, a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used.

Silver halide emulsions may be used unripe, but for use in schools, they are chemically sensitized before use. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a heterocyclic compound (JP-A-58-126526, JP-A-58-21).
No. 5644).

Photosensitive silver halide coating J used in the present invention
Amounts range from 1 tag to 10 g/rn' of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide. In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance.

Among such organic metal salts, organic silver salts are particularly preferably used.

Examples of organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include Japanese Patent Application No. 59-228551, page 37-
There are compounds described on page 39, columns 52 to 53 of US Pat. No. 4,500.626. Also, special application 1986-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in No. 13235, and
Acetylene silver described in 90089 is also useful. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0. Ol to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 501 mg to 10 mg in terms of silver.
g/rn” is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, Japanese Patent Publication Nos. 59-180550 and 60-1
No. 40335, Research Disclosure Magazine 197
The sensitizing dyes described in June 1988 issue, pages 12-13 (RD17029), JP-A-60-111239, Japanese Patent Application No. 1983
Examples include thermochromic sensitizing dyes described in No.-172967 and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
Substances exhibiting supersensitization may also be included in the emulsion (e.g., U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635.72).
No. 1, No. 3,743,510, No. 3,615,6
No. 13, No. 3,615,641, No. 3゜617.
No. 295 and No. 3,635,721).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4.225.666.

The amount added is generally 10-8 to 10-! per mole of silver halide. It is on the order of moles.

In the present invention, silver can be used as the image forming material. It may also contain a compound that generates or releases a mobile dye in response to or inversely to this reaction when silver ions are reduced to silver under high temperature conditions, that is, a dye-donating substance. can.

Examples of the dye-donating substances used in the present invention include:
Compounds that form pigments by oxidative coupling reactions (
couplers). This coupler is 4
It may be an equivalent coupler or a 2-equivalent coupler. Also,
Also preferred are 2-equivalent couplers which have a diffusion-resistant group as the m-group and form a diffusible dye through an oxidative coupling reaction. Specific examples of developers and couplers can be found in "The Theory of the Photographic Process" by James, 4th edition (T.H.).

James “The Theory of the
PhotographicProcess” ) 2
91-334 pages and 354-361 pages, Japanese Patent Application Publication No. 1983
No.-123533, No. 58-149046, No. 58
-1490475), No. 59-111148, No. 59
-124399, 59-174835, 59-
'231539, '59-231540, '60-
No. 2950, No. 60-2951, No. 60-14242
No. 60-23474, No. 60-66249, etc. Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (LI).

(D' J e −X ) n −Y
(L I ) Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, X represents a simple bond or a connecting group, and Y represents a photosensitive silver salt having a latent image in the form of an image. Correspondingly or inversely correspondingly, causing a difference in the diffusivity of the compound represented by (Dye-X)n-Y, or
Dye is released, and the released Dye and (Dye-X)n
-Y represents a group having the property of causing a difference in diffusivity, n represents 1 or 2, and when n is 2, the two Dye-Xs may be the same or different.

As a specific example of the dye-donating substance represented by the general formula (LI), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Pat. No. 3,134,769.
No. 3,362.819, No. 3,597,20
No. 0, No. 3,544,545, No. 3,482,9
It is described in No. 72, etc. Also, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction or U.S. Patent No. 3,9
80,479 etc., a substance that releases a diffusible dye through an intramolecular rewinding reaction of the isoxacilone ring was disclosed in JP-A No. 4.
No. 9-111.628, etc.

Another example is to make the dye-releasing compound into an oxidized form that does not have dye-releasing ability, coexist with a reducing agent or its precursor, and after development, it is oxidized and reduced by the remaining reducing agent to make it diffusible. A method for releasing a dye has also been devised, and specific examples of dye-donating substances used therein are disclosed in JP-A-53-110,827, JP-A-54-130,927,
It is described in No. 56-164.342 and No. 53-35.533. Japanese Patent Application No. 60-244,873 describes a compound that releases a diffusible dye when the N-0 bond is cleaved by a remaining reducing agent as a dye-donating substance that releases a diffusible dye using a similar mechanism. has been done.

Furthermore, as described in JP-A-59-185333, a donor-acceptor reaction occurs in the presence of a base and releases a diffusible dye, but when it reacts with an oxidized form of a reducing agent, dye release does not substantially occur. Non-diffusible compounds (LDA compounds) can also be used.

In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, there is a coupler that has a diffusible dye as a dissociative group, and a substance that releases a diffusible dye by reaction with an oxidized form of a reducing agent (DDR coupler). ) is British Patent No. 1,330.52
No. 4, Special Publication No. 48-39,165, British Patent No. 3゜4
No. 43.940, etc., and is preferably used in the present invention.

In addition, in methods using these reducing agents, image contamination due to oxidative decomposition products of the reducing agent becomes a serious problem. Release compounds (DRR compounds) have also been devised and are particularly advantageously used in the present invention. Representative examples are U.S. Pat. No. 3,928,312 and U.S. Pat.
No. 53,312, No. 4,055,428, No. 4,
No. 336.322, JP-A-59-65839, JP-A No. 59
-69839, 53-3819, 51-104
, No. 343, Research Disclosure Magazine 1746
No. 5, U.S. Patent No. 3,725.062, U.S. Patent No. 3.72
No. 8,113, No. 3,443.939, Japanese Unexamined Patent Publication No. 1983
It is a dye-donating substance described in US Pat. Specific examples of this type of dye-providing substance include the aforementioned U.S. Pat. No. 4,500,626, columns 2z-
Mention may be made of the compounds described in column 44, among which compounds (1) to (:l) described in the above-mentioned US patent,
(10) - (13), (16) - (!9), (28)
〜(30),(33)〜(35),(38)〜(40)
, (42)~/GJI^<h7 middle blindness, l8
Takashi Open your outward appearance go -ri AQA No. 68 No. 80
Compounds described on pages 1-87 are also useful. In addition, as dye-donating substances other than those mentioned above, dye silver compounds in which organic silver salts and dyes are combined (Research Disclosure magazine, May 1978 issue, pp. 54-58, etc.), heat-developable silver dye bleaching methods, etc. Azo dye used (U.S. Pat. No. 4.235
, No. 957, Research Disclosure Magazine, 197
6, April issue, pp. 30-32), leuco dyes (U.S. Pat. No. 3,985.565, U.S. Pat. No. 4,022,617, etc.) can also be used.

Hydrophobic additives such as the dye-providing compounds described above and the image-forming enhancers described below are disclosed in U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 7. In this case, JP-A-59
No. -83154, No. 59-178451, No. 59-1
No. 78452, No. 59-178463, No. 59-17
No. 8454, No. 59-178455, No. 59-178
A high boiling point organic solvent such as that described in No. 457 may be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing substance used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

Various surfactants can be used when dispersing hydrophobic substances into hydrophilic colloids.

For example, Nos. (37) to (3) of JP-A No. 59-157636.
The surfactants listed on page 8) can be used.

In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties.

Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include U.S. Pat.
Columns 49-50 of No. 500,626, No. 4,483,9
No. 14, columns 30-31, JP-A-60-140335, pages (■7)-(18), JP-A-60-128438
No. 60-128436, No. 60-128439, No. 60-128437, etc. can be used. Also, JP-A-56-138゜736, JP-A No. 57-
No. 40,245, US Pat. No. 4,330,617, and other reducing agent precursors can also be used.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Patent Nos. 4 and 5.
No. 00.626, columns 51-52.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples include Research Disclosure magazine, December 1978 issue 24-2.
Azoles and azaindenes described on page 5, JP-A-59
Nitrogen-containing carboxylic acids and phosphoric acids described in Japanese Patent Application No. 168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, Japanese Patent Application No. 1983-22
Acetylene compounds described in No. 8267 are used.

In the present invention, the photosensitive material may contain an image toning agent if necessary. Specific examples of effective toning agents include compounds described in Japanese Patent Application No. 59-268926, pages 92-93.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, it is necessary to use a light-sensitive element having at least three silver halide emulsion layers each sensitive to a different spectral region. good. For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each of these photosensitive layers may be divided into two or more layers, if necessary.

The photosensitive material used in the present invention may contain various additives known for use in heat-developable photosensitive materials and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, an antihalation layer, and a dye fixing layer. It can have a release layer, a matte layer, etc. to facilitate peeling off from the element. Various additives are listed in Research Disclosure Magazine, 1978, 6.
Plasticizers, matting agents, dyes for improving sharpness, which are described in pages 9 to 15 of the Japanese issue, Japanese Patent Application No. 59-209563, etc.
Additives include antihalation dyes, surfactants, optical brighteners, antislip agents, antioxidant IE agents, and antifading agents. In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. Each of the protective layer and the intermediate layer may be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent to prevent color fading and color mixing, an ultraviolet absorber, and a white pigment such as titanium dioxide. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of improving sensitivity.

The photographic material of the present invention is composed of a photosensitive element that forms or releases a dye by heat development and, if necessary, a dye fixing element that fixes the dye.

In particular, in systems that form images by diffusion transfer of dyes, a photosensitive element and a dye fixing element are essential, and in a typical form, the photosensitive element and dye fixing element are separately coated on two supports. It is broadly divided into two types: a form in which it is coated on the same support and a form in which it is coated on the same support. The relationship between the light-sensitive element and the dye-fixing element, the relationship with the support, and the relationship with the white reflective layer can be found in Japanese Patent Application No. 59-268926, pages 58-59, and U.S. Pat. No. 4,500,626, column 57. The relationships described in can also be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include those described in Japanese Patent Application No. 59-209563. The dye fixing element can be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer. One or more of the above layers may include a hydrophilic heat solvent, a plasticizer,
Antifading agents, UV absorbers, slip agents, matting agents, antioxidants, dispersed vinyl compounds for increasing dimensional stability, surfactants, optical brighteners, etc. may be included. In addition, especially in systems where thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is recommended to include a base and/or base precursor as described below in the dye fixing material in order to improve the shelf life of the photosensitive material. preferable. Examples of JL types of these additives are 1O of Japanese Patent Application No. 59-209563.
t (<-described on page 120.

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. Image formation promoters include promoting redox reactions between silver salt oxidizing agents and reducing agents;
It has functions such as promoting reactions such as generation of dye from dye-donating substance, decomposition of dye, and release of diffusible dye, and promotion of movement of dye from the light-sensitive material layer to the dye fixing layer. The functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents,
It is classified as a surfactant, a compound that interacts with silver or silver ions, etc. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For details of these, please refer to the patent application in 1983.
-213978, pages 67-71.

There are various other methods of generating bases, and the compounds used in these methods are all useful as base precursors. For example, a method of generating a base by mixing a sparingly soluble metal compound and a compound (referred to as a complex-forming compound) that undergoes a complex-forming reaction with the metal ions constituting the sparingly soluble metal compound, as described in Japanese Patent Application No. 169585/1985. There is also a method of generating a base by electrolysis as described in Japanese Patent Application No. 74702/1983.

The former method is particularly effective. Examples of poorly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, barium, and the like. Also,
Regarding complex-forming compounds, see, for example, N.E. Martell, R.M.-Smith (8, E., Martell, 1
1. M, 5w1Lh) co-author, “Critical Stability Constances”
llity Con5tants)4. It is detailed in Volumes 4 and 5, Plenum Press (PIenu+5Press). Specifically, aminocarboxylic acids, imidinoacetic acids, pyridylcarboxylic acids, aminophosphoric acids,
Carboxylic acids (mono, di, tri, and tetracarboxylic acids, as well as phosphino, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio,
Examples include salts of alkali metals, guanidines, amidines, or quaternary ammonium salts with compounds having substituents such as phosphino), hydroxamic acids, polyacrylates, and polyphosphoric acids.

It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive element and the dye-fixing element separately.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing material of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development, or interacts with silver and silver salt to stop development. It is an inhibitory compound. Specific examples include acid precursors that release acids when heated, electrophilic compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, patent application No. 58-216928, No. 59-
No. 48305, No. 59-85834 or No. 59-8
Compounds described in No. 5836, etc. ) Compounds that release mercapto compounds when heated are also used; for example, Japanese Patent Application No. 190173/1982
-268926, 59-246468, 60-
No. 26038, No. 60-22602, No. 60-260
There are compounds described in No. 39, No. 460-24665, No. 60-29892, and No. 59-176350.

A hydrophilic binder can be used for the photosensitive material and/or dye fixing material of the present invention. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as gelatin, proteins such as gelatin derivatives, cellulose derivatives, and natural substances such as starch, polysaccharides such as gum arabic, polyvinylpyrrolidone, Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Dispersed vinyl compounds, which are used in latex form and increase the dimensional stability of the photographic material, can also be used. These binders can be used alone or in combination.

In the present invention, the binder is applied in an amount of 20 g or less per bag, preferably 10 g or less, more preferably 7 g or less.
g or less is appropriate.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1 cc or less of solvent per 1 g of binder, preferably 0.
．． A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive material and/or dye fixing material of the present invention may contain an inorganic or organic hardening agent.

Specific examples of hardening agents can be found in Japanese Patent Application No. 59-268926, pages 94 to 95, and Japanese Patent Application Laid-open No. 59-157636 (
Examples include those described on page 38), and these can be used alone or in combination.

Further, in order to promote dye transfer, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature may be incorporated into the photosensitive material or dye fixing material.

The hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, the layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but it is preferably incorporated in the two dye fixing layers and/or a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alnyls, oximes, and other i-arylene rings. Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

The support used in the light-sensitive material and/or dye-fixing material of the present invention is one that can withstand processing temperatures. As general supports, glass, paper 5-polymer film, metal and their analogues are used, as well as Japanese Patent Application No. 59-268926, pages 95-96.
The supports listed on the page can be used.

The photosensitive material and/or the dye fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

The transparent or opaque heat-generating material in this case can be made using conventionally known techniques for producing resistive heat-generating elements.
As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder. Materials that can be used in these methods include those described in Japanese Patent Application No. 151,815/1984.

In the present invention, the method of coating the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer, and other layers is the method described in columns 55 to 56 of U.S. Pat. No. 4,500,626. is applicable.

As a light source for image exposure for recording an image on a photosensitive material, radiation including visible light can be used. In general, light sources 1 used for ordinary color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (LEDs), etc.
The light sources described on page 100 of No. 926 and column 56 of U.S. Pat. No. 4,500,626 can be used.

In the present invention, the steps of thermal development and dye transfer may be performed independently or simultaneously. Further, it may be continuous in the sense that development is followed by transfer in one step.

For example, after exposing a (+) photosensitive material imagewise and heating it,
There are two methods: (1) a method in which dye-fixing materials are stacked and heated if necessary to transfer the mobile dye to the dye-fixing material; and (2) a method in which a light-sensitive material is imagewise exposed, and the dye-fixing materials are stacked and heated.

The methods (1) and (2) above can be carried out in the substantial absence of water, or in the presence of a trace amount of water.

The heating temperature in the heat development step is about 0°C to about 250°C, but especially about 0°C to about IRQ"CMtf.
rn-'Ptr7. - When heating at the bottom left of the surface, the upper limit of the heating temperature is below the boiling point. When the transfer process is performed after the heat development process, the heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but in particular, it is 50°C or higher, which is about 10°C lower than the temperature in the heat development process. More preferably up to temperature.

A preferred image forming method in the present invention involves heating in the presence of a trace amount of water and a base and/or a base precursor after or simultaneously with image exposure, and at the same time as development, diffusion is generated in a portion corresponding to or inversely corresponding to a silver image. The coloring matter is transferred to the dye fixing layer. According to this method, the production or release reaction of the diffusible dye proceeds extremely quickly, and the movement of the diffusible dye to the dye fixing layer also proceeds rapidly, so that a high-density color image can be obtained in a short time.

The amount of water used in this R mode is at least 0.1 times, preferably 0.1 times or more, the weight of the total coating film of the photosensitive material and dye fixing material, and the amount of the solvent is equivalent to the maximum swelling volume of the total coating film. (In particular, the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film) may be used for cattle.

The state of the film when it swells is unstable, and depending on the conditions, it may cause local bleeding.To avoid this, use water equivalent to the volume at maximum swelling of the total coating film thickness of the photosensitive material and dye fixing material. It is preferable that the amount is less than or equal to . Specifically, the total surface M4 of the photosensitive material and dye fixing material is 1 per square meter.
A range of g to 50 g, especially 2 g to 35 g, and even more preferably 3 g to 25 g is preferred.

The base and/or base precursor used in this embodiment can be incorporated into both the light-sensitive material and the dye-fixing material.
It can also be supplied dissolved in water.

In the above embodiment, the image forming reaction system contains, as a base precursor, a basic metal compound that is sparingly soluble in water, and a compound that undergoes a complex formation reaction with metal ions constituting the sparingly soluble metal compound using water as a medium; Preferably, the pH of the system is raised by reaction of these two compounds upon heating.

Here, the image reaction system means a region where an image forming reaction occurs. Specifically, layers belonging to both the photosensitive element and the dye fixing element can be mentioned. If two or more layers are present, any of the layers may be used.

The poorly soluble metal compound and the complex forming compound need to be added at least in separate layers in order to prevent them from reacting before the development process. For example, in a so-called mono-sheet material in which a photosensitive element and a dye fixing element are provided on the same support, it is preferable that the above-mentioned two additive layers are separate layers, and one or more layers are interposed between them. A more preferred embodiment is one in which the poorly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. for example,
It is preferable that the poorly soluble metal compound is contained in the photosensitive element and the complex-forming compound is contained in the dye fixing element having a support separate from the photosensitive element. The complex-forming compound may be supplied after being dissolved in water to be coexisting. Hardly soluble metal compounds are disclosed in Japanese Patent Application Publication No. 5
6-174830, 53-102733, etc., and the average particle size is 50 microns or less.
Particularly preferred is 5 microns or less. The poorly soluble metal compound may be added to any layer of the photosensitive element, such as the photosensitive layer, intermediate layer, or protective layer, or may be added to two or more layers separately.

The amount of a poorly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the compounding process, particle size of the poorly soluble metal compound, complex-forming reaction rate, etc. It is appropriate to use it in an amount of 50% by weight or less, more preferably 0.01ffiff.
A range of i percent to 40 weight percent is useful. In addition, when the complex-forming compound is dissolved in water and supplied, 0.005 + so1 to 5
Concentrations of mol, especially 0.05 mof to 2 mol are preferred. Furthermore, in the present invention, the content of the N-Okino complex compound is 1/100 to 100 times, particularly 1710 to 20 times, in molar ratio to the content of the poorly soluble metal compound.
Double is preferred.

The method for adding water to the photosensitive layer or dye fixing layer is as follows:
For example, page 101, line 9 of Japanese Patent Application No. 59-268926.
There is a method described on page 102, line 4.

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, etc.
There is a means described in No. 68926, page 102, line 14 to page 103, line 11. It is also possible to apply a layer of conductive material such as graphite, carbon black, metal, etc. to the photosensitive element and/or dye fixing element, and heat the conductive layer directly by passing an electric current through it. good.

The pressure conditions and method of applying pressure when overlapping the photosensitive element and the dye fixing element and bringing them into close contact are described in Japanese Patent Application No. 59-2689.
The method described in No. 26, pages 103 to 104 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of the present invention. For example, JP-A-59-75247
Apparatuses described in Japanese Utility Model Application No. 59-177547, No. 59-181353, No. 60-18951, Utility Model Application No. 60-116734, etc. are preferably used.

V. Specific effects of the invention According to the invention, since it contains at least one photographic reagent represented by the general formula (I), it exists stably under storage conditions and is not required during processing. It is possible to obtain a silver halide photographic light-sensitive material that can promptly and efficiently release a photographically useful reagent at the appropriate timing.

In particular, the silver halide photographic light-sensitive material of the present invention has a pt+9 to 1
Timely release of photographically useful reagents is achieved even when processing with relatively low pl+ processing solutions of 2.

Further, in the present invention, desensitization and fogging caused by the addition of photographic reagents can be prevented, and the released photographically useful reagents can exert their functions. Furthermore, such photographic reagents are inexpensive and easily synthesized.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail.

Example 1 To evaluate the effectiveness of antifoggant precursors in the present invention, compounds of the present invention and their control compounds, Table 1 was prepared on a cellulose triacetate film support provided with a subbing layer. By applying an emulsion layer in which the antifoggant shown in 1 and the blocked antifoggant (antifoggant precursor) of the present invention are dissolved and emulsified in tricresyl phosphate together with the coupler (Op-1). , samples A-F were prepared. The coating amount of each substance is shown in parentheses as g/rn' or mol/m''.

(1) Emulsion layer Negative silver iodobromide emulsion, grain size 1.4μ (silver 1,
6x 10-'mol/rn") magenta coupler
Cp-1 (1,3X 10-3 mol/rn") tricresyl phosphate (0,15 g/rn") Antifoggant or its precursor (specified in Table 1) Gelatin (2,50 g/m") (2)
Protective layer gelatin (1.30g/rn')2.
4-dichloro-6-hydroxy-8-triazine sodium salt (0.05 g/ba) A tungsten light source was used for this photographic light-sensitive material, and the color temperature was adjusted to 4800" with a filter.
After giving the MS exposure, the temperature was increased to 38°C according to the following processing steps.
Development processing was performed.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Washing fixed for 2 minutes to seconds
Arrive 4 minutes 20 seconds Wash with water
Set for 3 minutes and 15 seconds
1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0g sodium sulfite 4.0g potassium carbonate
30.0g potassium bromide 1.4
g Potassium iodide 1.31 mg Hydroxylamine sulfate 2,434-(N-ethyl-N-β-hydroxyethylamino)-2 Monomethylaniline sulfate 4.5 g Add water
1.0ItpH10.0 Bleach liquid ethylenediaminetetraacetic acid Wn ferric ammonium salt 100.0g ethylenediaminetetraacetic acid disodium salt 10.0g ammonium bromide 150.0g ammonium nitrate
Add 10.0g water 1.0
ji4pH6.0 Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0d Sodium bisulfite 4.6g Add water
1. Oj! pH 6.6 stable liquid formalin (40%) 2.0at polyoxyethylene-p-1,000 tunonylphenyl ether (average degree of polymerization 10) Add 0.3g water
1.04! Table 1 shows the photographic properties of the thus processed products.

From Table 1, precursor compounds of the present invention were used. IB
-D, the fog is reduced with almost no decrease in sensitivity. On the other hand, in Sample E using the precursor compound described in Japanese Patent Publication No. 55-34927, the fog is reduced, but the sensitivity is greatly reduced. Also.

In sample F to which the antifogging agent was added, the sensitivity decreased significantly.

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

The comparative antifoggants and couplers used here are as follows.

Comparative Compound 1-A Compound described in Japanese Patent Publication No. 55-34927 Comparative Compound 1-B Example 2 Compounds of the present invention and their control (comparative) compounds were evaluated for the effectiveness of the auxiliary developer precursor in the present invention In order to do this, the auxiliary developers shown in Table 2 and their precursors were dissolved and emulsified in tricresyl phosphate together with the coupler (Cp-1) on a cellulose triacetate film support on which an undercoat layer was provided. Samples G to K were prepared by coating the emulsion layer added using the above method. The amount of each substance applied is g/rn” or mol/rn
' is shown in parentheses.

(1) Emulsion layer Negative silver iodobromide emulsion, grain size 1°4μ (silver 1.6 x 10-” mol/r
n") Magenta coupler Cp-1 (1,33X 10'mol/lo") Auxiliary developer or its precursor (1,33x 10-3 mol/rn") Tricresyl phosphate (0,15 g/ba) Gelatin ( (2,50 g/g) (2) Protective layer gelatin (130 g/g) 2,4-dichloro-6-hydroxy-3-triazine sodium salt (0,05 g/b) These film samples were heated at 40°C and relative humidity 70 % for 14 hours, sensitometric imagewise exposure was applied and color development was carried out in the same manner as in Example 1.

Table 2 shows the photographic properties of the product thus obtained.

As is clear from Table 2, the sample to which the auxiliary developer was added as it was resulted in increased fog and desensitization, but Sample H and Summer using the compound of the present invention were sensitized with almost no increase in fog.

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

2-A 2-B Example 3 In order to evaluate the effectiveness of the development stopper of the present invention in a thermal development system, compounds of the present invention and comparative compounds thereof were expressed on a polyethylene terephthalate support provided with an undercoat layer. Sample L-N was prepared by coating an emulsion layer in which the development inhibitor shown in 3 and the development stopper of the present invention were dissolved and emulsified in tricresyl phosphate together with the dye-donating compound (A). . The coating amount of each substance is shown in parentheses as g/rn" or mol/ln".

(1) Emulsion layer Negative silver iodobromide emulsion grain size 0.4μ (silver 400 sg/rn”)
Benzotriazole silver emulsion grain size o, tμ (Silver 100+sg/rn") Dye-donating substance (8) (300+sg/m") Tricresyl phosphate (150mg/m") Octaethylene glycol nonylphenol ether 7L/ (100mg/m") m") Development stopper or development inhibitor (2,5x 10= mol/rn") Gelatin (10
(2) Protective layer gelatin (800-g/ba) Zinc hydroxide particle size 0.3 μ (300 mg/rn”) 1.2
-bis(vinylsulfonylacetamido)ethane
(40 tags/bag) Dye-donating compound (^) Next, how to make the dye-fixing material will be described.

A dye-fixing material was prepared by coating it on a paper support laminated with polyethylene according to the composition shown in the table below.

After imagewise exposure for sensitometry was applied to the photosensitive material L-N, 8 cc/rn' of water was supplied to the film surface of the photosensitive material using a wire bar, and then the dye fixing material was stacked so that the film surface was in contact with the film surface. Combined. After heating for 20 seconds and 30 seconds using a heat roller whose temperature is adjusted so that the temperature of the water-absorbed film is 90°C, the dye fixing material is peeled off from the light-sensitive material, and a negative cyan image is obtained on the fixing material. It was done. The photographic properties obtained are shown in Table 3.

It can be seen that the compounds of the present invention do not inhibit development and provide images that are stable against fluctuations in processing time.

Example 4 In order to evaluate the effectiveness of the developer precursor of the present invention in a thermal development system, the developer shown in Table 4 was applied to a polyethylene terephthalate support provided with an undercoat layer to evaluate the compound of the present invention and its comparative compounds. Samples 0 to Q were prepared by coating an emulsion layer in which a precursor and a developer were dissolved and emulsified in tricresyl phosphate together with a dye-donating compound (0). The coating amount of each substance is shown in parentheses as mg/ba or mol/rn'.

(1) Emulsion layer Negative silver iodobromide emulsion Grain size: 0.4μ (400 trrg/rn of silver) Benzotriazole silver grain size: 0.1μ (took/rn” of silver) Dye-donating substance (B) (300mg/rn ”) Tricresyl phosphate (450mg/ln”) Octaethylene glycol nonylphenol ether (100mg/ln”) Dimethyl sulfamide (200mg/ln”) Developer or developer precursor (6X 10' mol/rn”) Gelatin (1000mg/ba) (2)
Protective layer Gelatin (800mg/lo) p-chlorophenylsulfonylacetate guanidine (800mg/lo") 1.2
-bis(vinylsulfonylacetamido)ethane
(40mg/rn”) Dye fixing material is Example 3
It was produced in the same manner as above except that the guanidicum picolinate salt was removed.

Dye-providing compound (B) 11+1 Light-sensitive materials O to Q were subjected to imagewise exposure for sensitometry, and then exposed to light for 20 minutes on a heat block heated to 150°C.
Heat evenly for seconds. Next, water is supplied to the film surface of the dye fixing material at 10 cc/goyer bar, and the film is brought into close contact with the film surface of the heat-developed photosensitive material. After passing through a beat roller heated to 80°C, the dye fixing material is When removed from the photosensitive material, a negative magenta image was obtained on the fixed material.
The photosensitive material was further stored at 50° C. for 4 days and then processed in the same manner. The photographic properties obtained are shown in Table 4.

It can be seen that the developer precursor of the present invention is heat developable and has excellent raw storage stability.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer has the following general formula (I):
A silver halide photographic light-sensitive material containing at least one photographic reagent represented by: General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc. group, alkynyl group, aralkyl group, aryl group or heterocyclic residue. R^3 and R^4 are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic residue, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, It represents a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylphosphoryl group, an arylphosphoryl group, or a sulfamoyl group. R^5 represents a hydrogen atom, or a substituted or unsubstituted acyl group, alkoxycarbonyl group, or aryloxycarbonyl group. Also, R^1 and R^2, R^1
and R^3, and R^3 and R^4, respectively, may be connected to each other to form a saturated or unsaturated ring, if possible. X represents an oxygen atom, a sulfur atom or an imino group. (time) represents a timing group, and t represents 0 or 1. PUG represents a halogen atom (in this case t=0) or a photographically useful group. }