JPH0922083A - Silver halide photographic sensitive material and developing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material which gives high contrast with a stable developer by incorporating at least one kind of specified compd. SOLUTION: This photosensitive material has at least one kind of silver halide emulsion layer and at least one kind of compd. expressed by formula. In formula, R1 and R2 are alkyl groups, R3 is an alkylene group, A is a bivalent connecting group, B is a group which cleaves from -NHNH- by the reaction with an oxidizing component of a developing agent during development under alkali conditions. Each group expressed by R1 to R3 , A, and B may have substituents. R1 and R2 or R2 and R3 may be bonded to form rings. Thereby, high contrast can be obtd. by using a stable developer, and the obtd. photographic sensitive material exhibits excellent sharpness, excellent dot quality, and high activity and the photographic quality does not decrease by black spots or the like. The photosensitive material shows little change in the quality even when it is stored for a long time and hardly gives bad effect on the environment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material capable of obtaining high contrast photographic characteristics.

[0002]

BACKGROUND OF THE INVENTION Conventionally, silver halide photographic light-sensitive materials have been widely used in photoengraving processes.

In the photolithography process, an original having a continuous tone is converted into a halftone image, that is, a density change of the original having a continuous tone is converted into a set of halftone dots having an area proportional to the density. The conversion is done.

In the step of converting the density change of the continuous tone original into a set of halftone dots having an area proportional to this density, a silver halide photographic light-sensitive material having a hard photographic property is used. A halftone image has been formed by photographing an original on a silver halide photographic light-sensitive material through an intersecting line screen or a contact screen and developing it.

In order to obtain a silver halide photographic light-sensitive material having a high contrast property, a silver halide photographic light-sensitive material has been hitherto disclosed as disclosed in JP-A-56-106244 and US Pat. No. 4,686,167. In addition, a compound such as hydrazine is contained as a contrast-increasing agent, and further, silver halide grains capable of effectively exhibiting the contrast-adjusting characteristics of these compounds are used, or other photographic additives are added to enhance the contrast. It was intended to obtain a silver halide photographic light-sensitive material having characteristics.

The silver halide photographic light-sensitive material thus obtained is certainly stable as a light-sensitive material, and a high-contrast photographic image can be obtained by processing with a developer capable of rapid processing. .

However, in these conventional silver halide photographic light-sensitive materials, when an original having continuous gradation is converted into a halftone dot image, sand-like or pin-like fog, so-called black spots are generated in the halftone dot. There is a problem that the quality of the dot image is impaired.

Further, such a silver halide photographic light-sensitive material had to be treated with a developer having a high pH of 11.1 or higher in order to effectively exhibit the characteristics of a compound such as hydrazine. pH as high as 11.1 or higher
The developing solution containing H has the problems that when exposed to air, the developing agent is oxidized and deteriorated, resulting in a decrease in sensitivity and the inability to obtain a high-contrast image.

In order to make up for this drawback, JP-A-63-29751, EP-A-333,435 and EP-A-345,025 disclose high contrast even when developed with a developer having a relatively low pH. There is disclosed a silver halide photographic light-sensitive material containing an active hydrazine type compound capable of obtaining various images. However, even if these compounds were used, the contrast was still insufficient and satisfactory halftone dot performance could not be obtained.

Further, European Patent No. 364,166, JP-A-62-222241, JP-A-60-140340 and JP-A-62-222241.
JP-A-250439 and JP-A-62-280733 describe adding a nucleation accelerator to the emulsion layer in order to promote high contrast. However, in the silver halide photographic light-sensitive materials obtained by these techniques, the generation of black spots is promoted, stable quality cannot be obtained, and the quality of halftone dot images is impaired.

[0011]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide photographic light-sensitive material capable of giving a high contrast by using a stable developing solution. The second purpose is
It is an object of the present invention to provide a processing method of a silver halide photographic light-sensitive material, which can obtain a high contrast even if the development processing is performed using a developing solution having a pH of 11.0 or less. A third object is to provide a silver halide photographic light-sensitive material having excellent sharpness and halftone dot quality. A fourth object is to provide a silver halide photographic light-sensitive material which is highly active and does not impair photographic quality due to black spots or the like. A fifth object is to provide a silver halide photographic light-sensitive material which has little quality variation even after storage with time. A sixth object is to provide a silver halide photographic light-sensitive material which does not have an adverse effect on the environment. A seventh object is to provide a hydrazine compound which is easy to synthesize and excellent in safety. An eighth object is to provide a hydrazine compound which gives a high-contrast photographic image even when processed with a developer capable of rapid processing. A ninth object is to provide a hydrazine compound which gives a stable photographic image even when the replenishing amount of the developing solution is small in the running processing of the silver halide photographic light-sensitive material.

[0012]

The above objects of the present invention are as follows: (1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer, represented by the following general formula (A1)
A silver halide photographic material comprising at least one compound represented by the formula:

[0013]

Embedded image [Wherein R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, A represents a divalent linking group, and B represents a reaction with an oxidized product of a developing agent during development under alkaline conditions. NHN
It represents a group that is cleaved from H-. R ₁ , R ₂ , R ₃ , A and B
Each group represented by may have a substituent.
R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. (2) The silver halide photographic light-sensitive material as described in (1) above, wherein the compound represented by the general formula (A1) is a compound represented by the following general formula (A2).

[0014]

Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, and B represents a group which is cleaved from —NHNH— by a reaction with an oxidized product of a developing agent during development under alkaline conditions. Each group represented by R ₁ , R ₂ , R ₃ and B may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. L, L ₁ and L ₂ represent an alkylene group, an arylene group or a divalent heterocyclic group,
J ₁ and J ₂ are —CO—, —SO ₂ —, —O—, —S—,
-CONH -, - NHCO -, - SO 2 NH -, - NH
_{SO 2 -, - NHCONH -,} - OCO -, - COO
-, -OCONH-, -NHCOO-, -NHCSNH
-, - it represents a NHSO ₂ NH-. k represents an integer of 0 or 1, m and n represent an integer of 0 to 4, and m or n is 2
In the above case, L ₁ and L ₂ , and J ₁ and J ₂ may be the same or different. (3) The silver halide photographic light-sensitive material described in (1) above, wherein the compound represented by the general formula (A1) is a compound represented by the following general formula (A3).

[0015]

Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, and A represents a divalent linking group. R ₁ , R ₂ , R
Each group represented by ₃ and A may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. G is -CO -, - COCO -, - SO 2
-, - SO -, - POR 4 -, represents an iminomethylene group, R ₄ represents an alkoxy group or an aryloxy group. D is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, -NR ₆ R _7, represent -OR _8, R ₆ and R ₇ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a cycloalkyl group R ₈ represents an alkyl group, an aryl group, a heterocyclic group, or a cycloalkyl group. D may also contain a moiety that causes a cyclization reaction that splits the -GD moiety from the rest of the molecule to produce a cyclic structure containing the atoms of the -GD moiety. -G-D as a whole, under alkaline conditions,
It is a group that is cleaved from —NHNH— by a reaction with an oxidized product of a developing agent during development. (4) The silver halide photographic light-sensitive material as described in (1) above, wherein the compound represented by the general formula (A1) is a compound represented by the following general formula (A4).

[0016]

Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, and R ₃ represents an alkylene group. Each group represented by R ₁ , R ₂ and R ₃ may have a substituent. In addition, R ₁ and R ₂ or R
₂ and R ₃ may combine to form a ring. L ₀ , L ₁ and L ₂
Represents an alkylene group, an arylene group or a divalent heterocyclic group, and J ₁ and J ₂ are —CO—, —SO ₂ —, —O—, —S.
-, - CONH -, - NHCO -, - SO 2 NH -, -
_{NHSO 2 -, - NHCONH -,} - OCO -, - CO
O-, -OCONH-, -NHCOO-, -NHCSN
H -, - represents a NHSO ₂ NH-. k represents an integer of 0 or 1, m and n represent an integer of 0-4. When m or n is 2 or more, L ₁ and L ₂ , and J ₁ and J ₂ may be the same or different. E represents a saturated heterocyclic group, and R ₅ represents a hydrogen atom or a group capable of substituting for a benzene ring. (5) The silver halide photographic light-sensitive material as described in (1) above, wherein the compound represented by the general formula (A1) is a compound represented by the following general formula (A5).

[0017]

[Chemical 21] [In the formula, R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, and A represents a divalent linking group. R ₁ , R ₂ , R
Each group represented by ₃ and A may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. G is -CO -, - COCO -, - SO 2
-, - SO -, - POR 4 -, represents an iminomethylene group, R ₄ represents an alkoxy group or an aryloxy group. Y represents a non-metal atomic group forming a 5- or 6-membered ring. R _a , R _b , R _c and R _d are a hydrogen atom, an alkyl group,
Represents an aryl group or an alkenyl group, Z is a group which, under alkaline conditions, undergoes a nucleophilic attack on -G- following the reaction with an oxidized product of a developing agent, causing splitting from the residual molecule, and causing a cyclization reaction with G. Represents p and q represent an integer of 0 or 1, and R _a , R _b , R _c , R _d , p and q may be the same or different. (6) In the silver halide photographic light-sensitive material having at least one silver halide emulsion layer, the following general formula (B1)
A silver halide photographic material comprising at least one compound represented by the formula:

[0018]

Embedded image[Wherein, R _{twenty one}Is an alkyl group, aryl group, or heterocyclic group
Represents, R_{twenty two}Represents a hydrogen atom, an alkyl group, or an aryl group.
You. X_TwoRepresents a hydrogen atom or a group capable of substituting on the thiophene ring.
You. ] (7) The compound represented by the general formula (B1) has the following general formula:
The above, which is a compound represented by (B2)
(6) The silver halide photographic light-sensitive material described in (6).

[0019]

Embedded image [In the formula, R ₂₂ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂₃ represents a hydrogen atom or a monovalent group. X ₂ represents a hydrogen atom or a group capable of substituting for the thiophene ring. L ₂₁ and L ₂₂
Represents an alkylene group, an arylene group or a divalent heterocyclic group, and J ₂₁ and J ₂₂ are —CO—, —SO ₂ —, —O—, —.
S-, -CONH-, -NHCO-, -NHCONH
-, -OCO-, -COO-, -OCONH-, -NH
COO -, - NHCSNH -, - representing the NHSO ₂ NH-. Y ₂ represents a hydrogen atom or a group capable of substituting on the benzene ring. k2 represents an integer of 0 or 1, m2 and n2 are 0 to 4
When m2 or n2 is 2 or more, L ₂₁ and L ₂₂ , J ₂₁ and J ₂₂ may be the same or different. (8) The silver halide photographic light-sensitive material as described in (6) above, wherein the compound represented by the general formula (B1) is a compound represented by the following general formula (B3).

[0020]

Embedded image [In the formula, R ₂₃ represents a hydrogen atom or a monovalent group. X ₂ represents a hydrogen atom or a group capable of substituting for the thiophene ring. L ₂₁ and L ₂₂ represent an alkylene group, an arylene group or a divalent heterocyclic group, and J ₂₁ and J ₂₂ represent —CO—, —SO ₂ —, —O.
-, -S-, -CONH-, -NHCO-, -NHCO
NH-, -OCO-, -COO-, -OCONH-,-
NHCOO -, - NHCSNH -, - NHSO 2 NH-
Represents Y ₂ represents a hydrogen atom or a group capable of substituting on the benzene ring. k2 represents an integer of 0 or 1, m2 and n2 are 0 to
Represents an integer of 4, and when m2 or n2 is 2 or more, L ₂₁ and L ₂₂ , J ₂₁ and J ₂₂ may be the same or different. (9) A silver halide photographic light-sensitive material is prepared by using the following general formula (A
1) to general formula (A5) or compounds represented by general formula (B1) to general formula (B3) in the presence of a developing agent having a pH of 11.0 or less. Development method.

[0021]

Embedded image [Wherein R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, A represents a divalent linking group, and B represents a reaction with an oxidized product of a developing agent during development under alkaline conditions. NHN
It represents a group that is cleaved from H-. R ₁ , R ₂ , R ₃ , A and B
Each group represented by may have a substituent.
R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. ]

[0022]

Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, and B represents a group which is cleaved from —NHNH— by a reaction with an oxidized product of a developing agent during development under alkaline conditions. Each group represented by R ₁ , R ₂ , R ₃ and B may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. L, L ₁ and L ₂ represent an alkylene group, an arylene group or a divalent heterocyclic group,
J ₁ and J ₂ are —CO—, —SO ₂ —, —O—, —S—,
-CONH -, - NHCO -, - SO 2 NH -, - NH
_{SO 2 -, - NHCONH -,} - OCO -, - COO
-, -OCONH-, -NHCOO-, -NHCSNH
-, - it represents a NHSO ₂ NH-. k represents an integer of 0 or 1, m and n represent an integer of 0 to 4, and m or n is 2
In the above case, L ₁ and L ₂ , and J ₁ and J ₂ may be the same or different. ]

[0023]

Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, and A represents a divalent linking group. R ₁ , R ₂ , R
Each group represented by ₃ and A may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. G is -CO -, - COCO -, - SO 2
-, - SO -, - POR 4 -, represents an iminomethylene group, R ₄ represents an alkoxy group or an aryloxy group. D is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, -NR ₆ R _7, represent -OR _8, R ₆ and R ₇ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a cycloalkyl group R ₈ represents an alkyl group, an aryl group, a heterocyclic group, or a cycloalkyl group. D may also contain a moiety that causes a cyclization reaction that splits the -GD moiety from the rest of the molecule to produce a cyclic structure containing the atoms of the -GD moiety. -G-D as a whole, under alkaline conditions,
It is a group that is cleaved from —NHNH— by a reaction with an oxidized product of a developing agent during development. ]

[0024]

Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, and R ₃ represents an alkylene group. Each group represented by R ₁ , R ₂ and R ₃ may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. L ₀ , L ₁ and L
₂ represents an alkylene group, an arylene group or a divalent heterocyclic group, and J ₁ and J ₂ are —CO—, —SO ₂ —, —O—, —
S -, - CONH -, - NHCO -, - SO 2 NH-,
_{-NHSO 2 -, - NHCONH -,} - OCO -, - C
OO-, -OCONH-, -NHCOO-, -NHCS
NH -, - represents a NHSO ₂ NH-. k represents an integer of 0 or 1, m and n represent an integer of 0-4. When m or n is 2 or more, L ₁ and L ₂ , and J ₁ and J ₂ may be the same or different. E represents a saturated heterocyclic group, and R ₅ represents a hydrogen atom or a group capable of substituting for a benzene ring. ]

[0025]

Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, and A represents a divalent linking group. R ₁ , R ₂ , R ₃
And each group represented by A may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. G is -CO-, -COCO-, -SO
_{2 -, - SO -, -} POR 4 -, represents an iminomethylene group, R ₄ represents an alkoxy group or an aryloxy group. Y represents a non-metal atomic group forming a 5- or 6-membered ring. R _a , R _b , R _c and R _d are a hydrogen atom, an alkyl group,
Represents an aryl group or an alkenyl group, Z is a group which, under alkaline conditions, undergoes a nucleophilic attack on -G- following the reaction with an oxidized product of a developing agent, causing splitting from the residual molecule, and causing a cyclization reaction with G. Represents p and q represent an integer of 0 or 1, and R _a , R _b , R _c , R _d , p and q may be the same or different. ]

[0026]

Embedded image[Wherein, R _{twenty one}Is an alkyl group, aryl group, or heterocyclic group
Represents, R_{twenty two}Represents a hydrogen atom, an alkyl group, or an aryl group.
You. X_TwoRepresents a hydrogen atom or a group capable of substituting on the thiophene ring.
You. ]

[0027]

Embedded image [In the formula, R ₂₂ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂₃ represents a hydrogen atom or a monovalent group. X ₂ represents a hydrogen atom or a group capable of substituting for the thiophene ring. L _21, L ₂₂ represents an alkylene group, an arylene group, a divalent heterocyclic group, J _21, J ₂₂ is _{-CO -, - SO 2 -,} - O -, - S
-, -CONH-, -NHCO-, -NHCONH-,
-OCO-, -COO-, -OCONH-, -NHCO
O -, - NHCSNH -, - it represents a NHSO ₂ NH-.
Y ₂ represents a hydrogen atom or a group capable of substituting on the benzene ring. k
2 represents an integer of 0 or 1, m2 and n2 represent integers of 0 to 4, and when m2 or n2 is 2 or more, L ₂₁ and L ₂₂ ,
J ₂₁ and J ₂₂ may be the same or different. ]

[0028]

Embedded image [In the formula, R ₂₃ represents a hydrogen atom or a monovalent group. X ₂ represents a hydrogen atom or a group capable of substituting for the thiophene ring. L ₂₁ and L ₂₂ represent an alkylene group, an arylene group or a divalent heterocyclic group, and J ₂₁ and J ₂₂ are —CO—, —SO ₂ —, —O—,
-S-, -CONH-, -NHCO-, -NHCONH
-, -OCO-, -COO-, -OCONH-, -NH
COO -, - NHCSNH -, - representing the NHSO ₂ NH-. Y ₂ represents a hydrogen atom or a group capable of substituting on the benzene ring. k2 represents an integer of 0 or 1, m2 and n2 are 0 to 4
When m2 or n2 is 2 or more, L ₂₁ and L ₂₂ , J ₂₁ and J ₂₂ may be the same or different. Is achieved.

The present invention will be described in detail below.

First, the general formulas (A1) to (A5) will be described.

In the general formulas (A1) to (A5), examples of the alkyl group represented by R ₁ and R ₂ include a linear or branched alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group. Is a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of the alkylene group represented by R ₃ include a linear or branched alkylene group having 1 to 20 carbon atoms, and preferably a linear or branched alkylene group having 1 to 8 carbon atoms.

In the general formula (A1), general formula (A3) and general formula (A5), A represents a divalent linking group, and R ₃ and-
There is no particular limitation as long as it is a group capable of connecting to NHNH-.

In the general formulas (A1) and (A2), B represents a group which is cleaved from --NHNH-- by a reaction with an oxidized form of a developing agent during development under alkaline conditions. -NHNH- is oxidized, and is subsequently cleaved and released by hydrolysis or intramolecular nucleophilic substitution reaction that occurs.

Each of the groups represented by R ₁ , R ₂ , R ₃ , A and B may have a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine). Atom), an alkyl group (for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms), an alkoxy group (for example, a linear, branched or cyclic alkyloxy group having 1 to 10 carbon atoms), Ester group (eg, alkoxycarbonyl group, aryloxycarbonyl group, acyloxycarbonyl group), aryl group (eg, phenyl group),
Examples thereof include an aryloxy group (eg, phenyloxy group), a carboxy group, a sulfoxy group, a nitro group, a cyano group, a hydroxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, and a urethane group. R ₁ and R ₂ , and R ₂ and R ₃ may be linked to each other to form a ring. Preferable rings formed by these include, for example, a piperidine ring, a pyrrolidine ring, a morpholine ring, a pyrazine ring, and a thiomorpho ring. Examples thereof include a phosphorus ring.

In the general formulas (A2) and (A4), the alkylene group represented by L, L ₀ , L ₁ and L ₂ is a linear or branched alkylene group having 1 to 8 carbon atoms. Among them, a straight chain or branched alkylene group having 1 to 4 carbon atoms is preferable. Examples of the arylene group include a phenylene group and a naphthylene group. Examples of the divalent heterocyclic group include pyridine, furan, thiophene, thiazole, oxazole,
Examples thereof include divalent groups such as pyrazole, pyrimidine, imidazole and thiadiazole.

J ₁ and J ₂ are --CO--, --SO ₂ -,-
O -, - S -, - CONH -, - NHCO -, - SO 2
_{NH -, - NHSO 2 -,} - NHCONH -, - OCO
-, -COO-, -OCONH-, -NHCOO-,-
NHCSNH -, - NHSO represents a ₂ NH-, these groups may be suitably selected from the viewpoint of easiness of safety and synthetic.

When m or n is 2 or more, L ₁ and L ₂ , J
₁ and J ₂ may be the same or different.

In the general formula (A3), G is -CO-,
_{-COCO, -SO 2 -, - SO} -, - POR 4 -, represents a iminomethylene, among this, -CO -, - COC
O- is preferred. R ₄ in —POR ₄ — represents an alkoxy group or an aryloxy group, and a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable.

The alkyl group represented by D includes a linear or branched alkyl group having 1 to 8 carbon atoms, the aryl group includes, for example, a phenyl group, and the heterocyclic group includes: For example, pyridine, furan,
Thiophene, thiazole, oxazole, pyrazole,
Examples of the monovalent group include pyrimidine, imidazole, thiadiazole, pyrrolidine, piperidine, pyrimidine, pyrazine, morpholine and tetrahydrofuran.
-NR ₆ R ₇ is represented by D, the -OR _8, R _6, R ₇
And the alkyl group represented by R ₈ has 1 carbon atom.
To 8 include linear or branched alkyl groups, examples of aryl groups include phenyl groups, examples of cycloalkyl groups include cyclohexyl groups, and examples of heterocyclic groups include pyridine groups. , Furan, thiophene, thiazole, oxazole, pyrazole, pyrimidine, imidazole, thiadiazole, pyrrolidine, piperidine, pyrimidine, pyrazine, morpholine, and a monovalent group of tetrahydrofuran.

D is a moiety that causes a cyclization reaction that splits the -GD moiety from the residual molecule to produce a cyclic structure containing the atoms of the -GD moiety, eg, a hydroxy group, a mercapto group, a carboxy group. It may have a sulfoxy group or a sulfonamide group.

-G-D as a whole is cleaved from -NHNH- by reaction with an oxidized product of a developing agent during development under alkaline conditions.

In the general formula (A4), examples of the saturated heterocycle represented by E include monovalent groups such as pyrrolidine, piperidine, pyrimidine, pyrazine, morpholine, tetrahydrofuran and thiomorpholine. Among these, monovalent groups such as pyrrolidine and piperidine are preferable.

In the general formula (A4), the group capable of substituting on the benzene ring represented by R ₅ is, for example, a halogen atom (eg, chlorine atom or bromine atom), an alkyl group (eg, 1 to 1 carbon atoms). 10 linear, branched or cyclic alkyl group), alkoxy group (for example, C 1-10 linear, branched or cyclic alkyloxy group), ester group (for example, alkoxycarbonyl group, aryloxycarbonyl group) , Acyloxycarbonyl group), carboxy group, sulfoxy group, nitro group, cyano group, hydroxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, urethane group and the like. R ₅ may be plural.

In the general formula (A5), examples of the 5- or 6-membered ring formed by Y include a benzene ring and a pyrazole ring.

The alkyl group represented by R _a , R _b , R _c and R _d is, for example, a methyl group, the aryl group is, for example, a phenyl group, and the alkenyl group is, for example. , Vinyl groups. R _a , R _b ,
Preferred as R _c and R _d is a hydrogen atom.

Z represents a group which undergoes a nucleophilic attack on -G- following the reaction with an oxidized product of a developing agent at the time of development under alkaline conditions to cause cleavage from the residual molecule and to cause a cyclization reaction with G.

Under alkaline conditions represented by Z, following the reaction with the oxidized form of the developing agent at the time of development, -G- is subjected to a nucleophilic attack to split from the residual molecule and to cause a cyclization reaction with G. , Known ones are used, for example, -O
_{H, -SH, -COOH, -NHSO 2} R 9 ( these groups are protected by a protecting group, hydrolysis by alkali or the like may be a group which is adapted to produce these groups.), R ₉ Are an alkyl group (eg, methyl group, ethyl group), an aryl group (eg, phenyl group, p
-Tolyl group) and a heterocyclic group (for example, a cenyl group).

The compounds represented by the general formulas (A1) to (A5) can be easily synthesized by applying a conventionally known method.

The following are the general formulas (A1) to (A5).
The representative synthetic routes of the compounds represented by are shown below, but the synthetic routes of the compounds represented by the general formulas (A1) to (A5) are not limited thereto.

[0050]

Embedded image

[0051]

Embedded image Specific examples of the compounds represented by the general formula (A1) to the general formula (A5) will be given below, but the general formula (A1) to the general formula (A).
The compound represented by 5) is not limited to these.

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

<Synthesis Example-1 (Synthesis of Compound H-3)>
3.3 g of 1- (β- (4-amino-2,2,6,6-tetramethylpiperidin-4-yl) oxalyl) -2- (4-aminophenyl) hydrazine was added to 80 g of acetic acid and 1.2 g of sodium acetate. Dissolve and react under reaction conditions of 20 ° C or less
-(Α- (3-N, N-diethylaminopropylthio)
Acetamide) benzenesulfonyl chloride (4.6 g) was added little by little and the same temperature was maintained for 1 hour.

The reaction solution was added to 240 cc of water, and the precipitated crystals were filtered, washed with water and dried. The obtained crude crystals were purified by silica gel column chromatography. Yield 1.8 g Structure determined using NMR and MASS.

<Synthesis Example-2 (Synthesis of Compound H-22)> 1- (2-hydroxymethylbenzoyl) -2-
2.6 g of (4-aminophenyl) hydrazine was added to 80 c of acetic acid.
c) and 1.2 g of sodium acetate and add 4.7 g of m- (α- (2-thiamorpholinoethylthio) acetamido) benzenesulfonyl chloride little by little under the reaction condition of 20 ° C or less, and the same temperature for 1 hour. Held

The reaction solution was added to 240 cc of water, and the precipitated crystals were filtered, washed with water and dried. The obtained crude crystals were purified by silica gel column chromatography. Yield 3.0 g Structure was determined using NMR and MASS.

Next, the general formulas (B1) to (B3) will be described.

In the general formula (B1), R _{twenty one}Represented by
The alkyl group may be a straight chain or branched chain having 1 to 20 carbon atoms.
A variety of alkyl groups can be mentioned, but preferably a carbon atom.
It is a linear or branched alkyl group of the number 4 to 16. Ally
Examples of the ru group include a phenyl group and a naphthyl group.
Can be Examples of the heterocyclic group include pyridine and fura.
Amine, thiophene, thiazole, oxazole, pyrazol
Monovalent of le, pyrimidine, imidazole and thiadiazole
Groups.

Examples of the alkyl group represented by R ₂₂ include a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 8 carbon atoms. Is. Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the group capable of substituting the thiophene ring represented by X ₂ include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkyl group (eg, a straight chain having 1 to 10 carbon atoms). , Branched or cyclic alkyl groups),
Aryl group (for example, phenyl group, naphthyl group), alkoxy group (for example, linear, branched or cyclic alkyloxy group having 1 to 10 carbon atoms), ester group (for example, alkoxycarbonyl group, aryloxycarbonyl group,
(Acyloxycarbonyl group), carboxy group, sulfoxy group, nitro group, cyano group, hydroxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, urethane group and the like. X ₂
May be plural.

R _{twenty one}, R_{twenty two}And X_TwoEach group represented by
May have a substituent.

[0067] In the general formula _{(B2), R 22, X} 2 is in the formula (B1) and R _22, X ₂ respectively the same.

Examples of the monovalent group represented by R ₂₃ include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkyl group (eg, straight chain, branched chain or branched chain having 1 to 10 carbon atoms). Cyclic alkyl group), aryl group (eg, phenyl group, naphthyl group), alkoxy group (eg, linear, branched or cyclic alkyloxy group having 1 to 10 carbon atoms), ester group (eg, alkoxycarbonyl group) , Aryloxycarbonyl group, acyloxycarbonyl group), carboxy group, sulfoxy group, nitro group, cyano group, hydroxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, urethane group and the like.

Examples of the group capable of substituting on the benzene ring represented by Y ₂ include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkyl group (eg, a straight chain having 1 to 10 carbon atoms). , Branched or cyclic alkyl groups),
Aryl group (for example, phenyl group, naphthyl group), alkoxy group (for example, linear, branched or cyclic alkyloxy group having 1 to 10 carbon atoms), ester group (for example, alkoxycarbonyl group, aryloxycarbonyl group,
(Acyloxycarbonyl group), carboxy group, sulfoxy group, nitro group, cyano group, hydroxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, urethane group and the like. Y ₂
May be plural.

Examples of the alkylene group represented by L ₂₁ and L ₂₂ include linear or branched alkylene groups having 1 to 8 carbon atoms, preferably linear or branched ones having 1 to 4 carbon atoms. Is an alkylene group. Examples of the arylene group include a phenylene group and a naphthylene group. Examples of the divalent heterocyclic group include pyridine, furan, thiophene, thiagall, oxazole,
Examples thereof include divalent groups such as pyrazole, pyrimidine, imidazole and thiadiazole.

J ₂₁ and J ₂₂ are --CO--, --SO _2- ,
-O-, -S-, -CONH-, -NHCO-, -NH
CONH-, -OCO-, -COO-, -OCONH
-, - NHCOO -, - NHCSNH -, - NHSO 2
Although it represents NH-, these groups may be appropriately selected from the viewpoints of safety and ease of synthesis.

When m or n is 2 or more, L ₂₁ and L ₂₂ ,
J ₂₁ and J ₂₂ may be the same or different.

In the general formula (B3), X ₂ has the same meaning as X ₂ in the general formula (B1), and R ₂₃ , Y ₂ , L ₂₁ ,
L ₂₂ , J ₂₁ and J ₂₂ are R ₂₃ and Y in the general formula (B2).
₂ , synonymous with L ₂₁ , L ₂₂ , J ₂₁ and J ₂₂ .

When m or n is 2 or more, L ₁ and L ₂ , J
₁ and J ₂ may be the same or different.

The compounds represented by the general formulas (B1) to (B3) can be easily synthesized by applying a conventionally known method.

Below, the general formula (B1) to the general formula (B3)
The representative synthetic routes of the compounds represented by are shown below, but the synthetic routes of the compounds represented by the general formulas (B1) to (B3) are not limited thereto.

[0077]

Embedded image Specific examples of the compounds represented by the general formula (B1) to the general formula (B3) are shown below, and the general formula (B1) to the general formula (B
The compound represented by 3) is not limited to these.

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

<Synthesis Example-3 (Synthesis of Compound T-7)> 5
1.6 g of -amino-2-formylhydrazinothiophene was dissolved in 50 cc of acetic acid and 1.0 g of sodium acetate, and 3- (α- (4-chlorobenzhydrylthio) acetamido) benzenesulfonyl chloride 5.2 was added under the reaction conditions of 20 ° C or lower.
g was added in small portions and kept at the same temperature for 1 hour.

The reaction solution was added to 200 cc of water, and the precipitated crystals were filtered, washed with water and dried. The obtained crude crystals were purified by silica gel column chromatography. Yield 2.0g.

The structure was determined using NMR and MASS. <Synthesis Example-4 (Synthesis of Compound T-9)> 5-Amino-2
-Dissolve 1.6g of formylhydrazinothiophene in 50cc of acetic acid and 1.0g of sodium acetate, and add 5g under reaction conditions below 20 ℃.
6.2 g of-([alpha] -cyclohexylthiotetradecanoamido) thienyl-2-sulfonyl chloride was added in small portions and the same temperature was maintained for 1 hour.

The reaction solution was added to 200 cc of water, and the precipitated crystals were filtered, washed with water and dried. The obtained crude crystals were purified by silica gel column chromatography. Yield 1.8g.

The structure was determined using NMR and MASS.

In the present invention, in the case of effectively promoting the contrast enhancement by the hydrazine derivative represented by the general formula (A1) to the general formula (A5) or the general formula (B1) to the general formula (B3), A nucleation accelerator can be used.
Preferred nucleation accelerators include compounds represented by the following general formula (Na) or general formula (Nb).

[0087]

Embedded image [In the formula, R ₁₀ , R ₁₁ and R ₁₂ represent a hydrogen atom or an alkyl group. R ₁₀ and R ₁₁ or R ₁₁ and R ₁₂ are linked to each other and 5
May form a 8-membered to 8-membered ring. ]

[0088]

Embedded image [In the formula, R ₁₃ and R ₁₄ represent a hydrogen atom, a substituted or unsubstituted aromatic group or a heterocyclic group. In the general formula (Na), examples of the alkyl group represented by R ₁₀ , R ₁₁ and R ₁₂ include a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms.

Preferable substituents in the above substituted alkyl group include, for example, halogen atom (eg, chlorine atom, bromine atom), alkyl group (eg, having 1 to 1 carbon atoms).
10 linear or branched or cyclic alkyl group), aryl group (eg, phenyl group, naphthyl group), alkoxy group (eg, linear or branched or cyclic alkyloxy group having 1 to 10 carbon atoms), aryl Oxy group (for example, phenoxy group), ester group (for example, alkoxycarbonyl group, aryloxycarbonyl group, acyloxycarbonyl group), carboxy group, sulfoxy group, nitro group, cyano group, hydroxy group, acylamino group, sulfonamide group, Carbamoyl group, sulfamoyl group,
Examples thereof include ureido group and urethane group.

Further, these compounds may have a silver halide adsorbing group in the molecule. Examples of the preferable adsorptive group include a heterocyclic group, a mercapto group, a thioether group, a thione group and a thiourea group.

Specific examples of the compound represented by formula (Na) are shown below.

[0092]

Embedded image

[0093]

Embedded image

In the general formula (Nb), examples of the aromatic group represented by R ₁₃ and R ₁₄ include a phenyl group and a naphthyl group, and a phenyl group is preferable. Examples of the heterocyclic group include a thiophene group, a pyridine group, and a furan group, and a pyridine group is preferable.

Preferable substituents in the substituted aromatic group or substituted heterocyclic group include, for example, halogen atom (eg, chlorine atom, bromine atom), alkyl group (eg, straight chain or branched chain having 1 to 10 carbon atoms or Cyclic alkyl group), aryl group (eg, phenyl group, naphthyl group), alkoxy group (eg, linear or branched or cyclic alkyloxy group having 1 to 10 carbon atoms), aryloxy group (eg, phenoxy group) ), Ester group (eg, alkoxycarbonyl group, aryloxycarbonyl group, acyloxycarbonyl group), carboxy group, sulfoxy group, nitro group, cyano group, hydroxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido Group, urethane group and the like.

Further, these compounds may have a silver halide adsorbing group in the molecule. Examples of the preferable adsorptive group include a heterocyclic group, a mercapto group, a thioether group, a thione group and a thiourea group.

Specific examples of the compound represented by formula (Nb) are shown below.

[0098]

Embedded image

The hydrazine derivative represented by the general formula (A1) to the general formula (A5) and the general formula (B1) to the general formula (B3) and the nucleation accelerator that effectively promotes the contrast enhancement by the hydrazine derivative are Any layer can be used as long as it is on the silver halide emulsion layer side, but it is preferably used for the silver halide emulsion layer or its adjacent layer. The preferable addition amount varies depending on the grain size of the silver halide grains, the halogen composition of the silver halide emulsion, the degree of chemical sensitization, the kind of the inhibitor, etc., but is generally 10 per mol of silver halide. ^-6 to 10 ^-1 mol range is preferred, especially 10
A range of ^-5 to 10 ^-2 mol is preferred.

When the hydrazine derivative represented by the general formula (A1) to the general formula (A5) and the general formula (B1) to the general formula (B3) and the nucleation accelerator are added to the silver halide emulsion layer, halogenation is performed. Any time of producing a silver emulsion, for example,
It can be added during the formation of the silver halide grains, after the grain formation and before the chemical sensitization, or after the chemical sensitization and the coating. It is also possible to add it by spraying or coating a solution containing a hydrazine derivative and a nucleation accelerator after coating a silver halide emulsion layer or other photographic constituent layers.

The hydrazine derivative represented by the general formula (A1) to the general formula (A5) and the general formula (B1) to the general formula (B3) and the nucleation accelerator are various solvents (eg, water, methanol, ethanol). , Acetone, ethyl acetate, dimethylformamide, various high boiling point solvents, etc.) and added to the silver halide emulsion layer and other photographic constituent layers. Alternatively, it may be added in the form of a dispersion solution obtained by dissolving in a solvent and then performing ultrasonic dispersion or media dispersion such as ball milling together with the gelatin solution. As yet another addition method, the hydrazine derivative represented by the general formula (A1) to the general formula (A5) and the general formula (B1) to the general formula (B3) and the nucleation accelerator are dissolved in a solvent and then the pH is increased. And the like, and the resulting solid fine particles are subjected to media dispersion with a ball mill or the like, and added using the formed solid fine particles.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited in the halogen composition of silver halide grains, but is preferably silver chloride, 60 mol%.
It is composed of silver chlorobromide containing the above silver chloride or silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide grains is 1.2.
It is preferably not more than μm, and particularly preferably 0.8 to 1.0 μm. The term average particle size is commonly used by experts in the field of photographic science. The particle size means the particle diameter when the particles are spherical or can be approximated to a sphere. When the particle is a cube, the cube is converted into a sphere having the same volume, and the diameter of the sphere is the particle size. See Mies, James: The for details on how to find the average particle size.
Theory of the Photographic Process (CEMees & T.H. James: The theory of the photogr
aphic process) 3rd edition, pp. 36-43 (1966 (published by McMillan "Mcmillan")).

The shape of the silver halide grains is not limited.
It may have a flat plate shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedron shape, or any other shape. Further, the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention preferably has a narrow grain size distribution, and particularly 90% of the total number of grains, preferably ± 40% of the average grain size. Is 95
A so-called monodisperse emulsion having a percentage of 100% is preferable.

When a soluble silver salt and a soluble halogen salt are reacted to form a silver halide emulsion, any method such as a one-sided mixing method, a simultaneous mixing method or a combination thereof may be used.

A method of forming emulsion grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. A regular and nearly uniform grain size silver halide emulsion is obtained.

The silver halide emulsion comprises at least one of the process of forming grains and the process of growing grains in which cadmium salt, zinc salt, lead salt, thallium salt, rhenium salt, ruthenium salt, osmium salt, iridium salt or rhodium salt is used. Alternatively, it is preferable to add a complex salt containing these elements. The ligands forming these complex salts include nitrosyl ligands, thionitrosyl ligands, aco ligands,
Cyanide ligands, cyan oxide ligands and halide ligands (eg chloro ligands, bromine ligands) are preferred.

For the silver halide emulsion and its preparation method, see Research Discl.
No. 176, 17643, pp. 22-23 (December 1978), or in the references cited therein.

The silver halide emulsion may or may not be chemically sensitized. As the chemical sensitization method, a sulfur sensitization method,
The selenium sensitization method, tellurium sensitization method, reduction sensitization method and noble metal sensitization method are known, and any one of them may be chemically sensitized alone or in combination. May be. As the sulfur sensitizer, a known sulfur sensitizer can be used,
Preferred sulfur sensitizers include sulfur compounds contained in gelatin, as well as various sulfur compounds such as thiosulfates, thioureas, rhodanins, and polysulfide compounds. As the selenium sensitizer, a known selenium sensitizer can be used. For example, the compounds described in US Pat. No. 1,623,499, JP-A-50-71325 and JP-A-60-150046 can be preferably used.

As the tellurium sensitizer, known tellurium sensitizers can be used. For example, U.S. Patent No. 1,623,49
The compounds described in No. 9, No. 3,772,031, No. 3,320,069 and the like can be preferably used.

As a noble metal sensitizing method, a gold sensitizing method is typical, and a gold compound, mainly a gold complex salt is used for the gold sensitizing method. As the noble metal sensitizing method, noble metals other than gold, such as platinum, palladium and rhodium, can be used.

As the reduction sensitizer, stannous salt, amines, formamidine sulfinic acid, silane compound and the like can be used.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. These pigments include:
As the basic heterocyclic nucleus, any of the nuclei usually used for cyanine dyes can be used. 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 and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, A quinoline nucleus or the like can be used. These nuclei may have a substituent on a carbon atom. Merocyanine dyes or complex merocyanine dyes include, as nuclei having a ketomethylene structure, pyrazolin-5-one nuclei, thiohydantoin nuclei, and 2-thiooxazolidin-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5 to 6 membered heterocyclic ring such as a rhodanine nucleus or a thiobarbituric acid nucleus can be applied. Specifically, research
Research Disclosure Volume 176 1
7643 (December 1978 issue) pages 2-3, U.S. Pat. No. 4,425,425
No. 4,425,426 can be used.

The sensitizing dye can be used by dissolving it using ultrasonic vibration as described in US Pat. No. 3,485,634. In addition, as a method for dissolving or dispersing a sensitizing dye and adding it to an emulsion, U.S. Pat.Nos. 3,482,981 and 3,585,195, and 3,
469,987, 3,425,835, 3,342,
No. 605, British Patent No. 1,271,329, No. 1,03
No. 8,029, No. 1,121,174, U.S. Pat.
There are methods described in the specifications of 660,101 and 3,658,546. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Useful combinations of dyes that exhibit supersensitization and substances that exhibit supersensitization are described in Research Disclosure (Research D
isclosure) Volume 176 17643 (issued December 1978) Page 23, IV, Item J.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles, for example, benzothiazolium salt, nitroindazole cheek,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles ( In particular, 1-phenyl-5-mercaptotetrazole) and the like;
Mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3
a, 7-Tetrazaindenes), pentazaindenes, etc .; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers such as benzenesulfonic acid amide and the like can be added.

The light-sensitive emulsion layer and the non-light-sensitive hydrophilic colloid layer of the light-sensitive material used in the present invention can be hardened by using an inorganic or organic hardener. Examples of these inorganic or organic hardeners include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), Dioxane derivative (2,3-dihydroxydioxane, etc.), active vinyl compound (1,3,3)
5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) ), Isoxazoles, dialdehyde starches, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activating type hardeners and the like can be used alone or in combination. Among them, a preferable hardener is a carboxyl group-activated hardener, and specifically,
56-12853, 58-32699, JP-A-49-51945, 61-9641 and 63-61254, the hardener represented by the general formula (a). , A carbamoyl ammonium-based hardener described in JP-A 1-270046,
Hardeners described in Belgian Patent No. 825726, JP-A-60-225148, Amidinium-based hardeners described in JP-A-61-240236, JP-A-51-126125, 52-
Carboxydiimide type hardeners described in 48311, etc., JP-B-58-50699, JP-A-57-44140,
Examples include pyridinium salt-based hardeners described in JP-A-57-46538 and 52-54427, and hardeners represented by the general formula (b) described in JP-A-63-61254. To be Among them, a more preferable hardener is a carbamoylammonium hardener represented by the general formula (I) described in JP-A 1-270046.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention may be used for various purposes such as improvement of coating property, antistatic property, slip property improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Various known surfactants may be used.

Gelatin is advantageously used as the binder or protective colloid of the silver halide emulsion, 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 and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. be able to.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with them. Acid, methacrylic acid, α,
β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)
Acrylate, sulfoalkyl (meth) acrylate,
A polymer having a monomer component of a combination of styrene sulfonic acid and the like can be used.

Various other additives can be used in the light-sensitive material of the present invention. Examples of these additives include desensitizers, plasticizers, slip agents, development accelerators, oils,
Examples include dyes.

Regarding these additives and the above-mentioned additives, specifically, Research Disclosure (Rese
Arch Disclosure) No. 176 (supra), pages 22-31, etc. can be used.

In the light-sensitive material of the present invention, the emulsion layer and the protective layer may be a single layer or multiple layers composed of two or more layers.
In the case of a multilayer, an intermediate layer or the like may be provided therebetween. In the light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed by coating on one side or both sides of a flexible support usually used for light-sensitive materials. Useful as the flexible support is a film made of a synthetic polymer of cellulose acetate, cellulose acetate / butyrate, polystyrene, or polyethylene terephthalate.

Examples of the developing agent or auxiliary developing agent that can be used in the development of the light-sensitive material of the present invention include dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone. , 2,5-dimethylhydroquinone, etc.), 3-pyrazolidones (eg, 1-phenyl-3
-Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3 -Pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-p-aminophenol, N-methyl-p-aminophenol, 2,
4-diaminophenol etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (for example, 1
-(P-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p- Amino-N-methylphenyl)-
3-aminopyrazoline, etc.), transition metal complex salts (Ti,
Complex salts of transition metals such as V, Cr, Mn, Fe, Co, Ni and Cu. These may be of a form having a reducing power for use as a developing solution, such as Ti ³⁺ , V ²⁺ , Cr ²⁺ ,
It takes the form of a complex salt such as Fe ²⁺ , and as the ligand, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, hexametapolyphosphoric acid, tetrapolyphosphoric acid, etc. Examples thereof include phosphoric acid and salts thereof. ) And the like can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes, a combination of aminophenols and dihydroxybenzenes, or a combination of 3-pyrazolidones and ascorbic acid. It is preferably used in combination, aminophenols and ascorbic acid, 3-pyrazolidones and transition metal complex salts, and aminophenols and transition metal complex salts. The developing agent is usually 0.01
It is preferably used in an amount of ˜1.4 mol / l.

In the present invention, silver sludge-preventing agents can be used. As these silver sludge-preventing agents, Japanese Patent Publication No. 62-4702, JP-A-3-51844, and No. 4-26838 can be used.
The compounds described in JP-A Nos. 4-362942, 1-319031 and the like can be mentioned.

The developing waste liquid generated by the development can be regenerated by energizing, for example. Specifically, the development waste liquid tank and the electrolyte solution tank are arranged so as to be in contact with each other via an anion exchange membrane, and the cathode (for example, an electric conductor such as stainless wool or a semiconductor) is placed in the development waste liquid tank.
In an electrolytic solution bath, and an anode (for example, carbon, gold, platinum,
A non-dissolving electric conductor such as titanium) is put in and both electrodes are energized for regeneration.

The light-sensitive material according to the present invention can be processed while electricity is supplied. At that time, various additives added to the developer, for example, preservatives, alkali agents, pH buffers, sensitizers, antifoggants, which can be added to the developer,
A silver sludge inhibitor may be additionally added.

When the developing waste liquid is regenerated and used, it is preferable to use transition metal complex salts as a developing agent.

A preservative is used in the developer. As the preservative, sulfite, and as metabisulfite, sodium sulfite, potassium sulfite, ammonium sulfite, sodium metabisulfite and the like are used. When sulfite is used as a preservative, the addition amount of sulfite is preferably 0.25 mol / liter or more. Particularly preferably 0.4 mol /
More than a liter.

In the developer, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) , Solubilizers (eg, polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg, polyoxyethylene-containing nonionic surfactants, quaternary ammonium compounds, etc.), surfactants, quenchers Foaming agents, antifoggants (eg, halides such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg, ethylenediamine) Tetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate ), A development accelerator (for example, compounds described in U.S. Pat. No. 2,304,025 and JP-B-47-45541), a hardener (for example, glutaraldehyde or a bisulfite adduct thereof), an antifoaming agent. Agents and the like can be added. The pH of the developer is preferably adjusted to 11.0 or less, more preferably 8.5 to 10.5.

In the present invention, a silver halide photographic light-sensitive material is added with a hydrazine derivative represented by the general formula (A1) to the general formula (A5) or the general formula (B1) to the general formula (B3). The effect of the present invention can be obtained even if the development is performed.

In the present invention, as a method of developing a silver halide photographic light-sensitive material, a developing agent in a light-sensitive material, for example,
In the case where the method of incorporating in the emulsion layer and processing the light-sensitive material in an alkaline aqueous solution for development is employed, the compound represented by the general formula (A
1) to general formula (A5) and general formula (B1) to general formula (B)
The hydrazine derivative represented by 3) may be contained in the activator treatment liquid.

Such a developing treatment is often used as one of rapid processing methods for a light-sensitive material in combination with a silver salt stabilizing treatment with a thiocyanate, and is also applicable to such a processing solution. It is possible. In the case of such rapid processing, the effect of the present invention is particularly large.

For fixing the light-sensitive material of the present invention, a fixing solution having a generally used composition can be used. The fixer is generally an aqueous solution containing a fixer and others, and usually has a pH of 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, etc. can be added to the fixing solution.

If desired, the fixer may contain preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid), pH adjusters (eg, sulfuric acid), and chelates capable of softening water. Compounds such as agents may be included.

Each component of the developing solution may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid in a semi-kneaded state with high viscosity. The developing solution may be used as it is by dissolving each component, or a concentrated solution may be prepared in advance and diluted before use. Alternatively, it may be used as it is.

In the present invention, in developing processing,
The developing temperature can be set in the range of 20 to 30 ° C. which is a normal developing temperature, or can be set in the range of high temperature processing of 30 to 40 ° C.

An automatic developing machine is preferably used for the development processing of the silver halide photographic light-sensitive material of the present invention. Development processing using an automatic developing machine is performed while replenishing a fixed amount of development replenisher proportional to the area of the processed light-sensitive material.
The replenishment amount of the development replenisher is 1 m ² to reduce the amount of waste liquid.
It is preferable to keep it below 300 ml per 1 m ²
More preferably, it is 75 to 200 milliliters.

In recent years, there has been a demand from the user to shorten the developing time. When developing a black-and-white photosensitive material by the developing method of the present invention using an automatic developing machine, the leading edge of the film is inserted into the automatic developing machine. It is preferable to set the total processing time (Dry to Dry) from 10 to 60 seconds from the time to exit the drying zone. The total processing time referred to here includes the total process time required to process the black and white photosensitive material, and specifically,
A time that includes all the steps required for processing, such as development, fixing, bleaching, washing, stabilizing, and drying, that is, automatic development of the exposed black and white photosensitive material that is dry It is the time from insertion into the machine to obtaining a dry imaged photographic material. If the total processing time is less than 10 seconds, satisfactory photographic performance may not be obtained due to desensitization and softening. A more preferable total processing time (Dry to Dry) is 15 to 50 seconds.

The automatic processor is a heat transfer member heated to 90 ° C. or higher (for example, a heat roller at 90 ° C. to 130 ° C.) or 1
A radiant object (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, etc.) that directly emits heat to radiate radiation or heat energy from a resistance heating element To a radiator such as copper, stainless steel, nickel, and various ceramics to emit infrared rays).

[0142]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (Preparation of Silver Halide Emulsion A) A silver chlorobromide emulsion consisting of 70 mol% of silver chloride and 30 mol% of silver bromide was prepared by the simultaneous mixing method. During simultaneous mixing, K ₃ RhBr ₆ was added at 8.1 × 10 ^-8 mol per mol of silver. The obtained emulsion consisted of cubic silver halide grains and contained monodisperse grains (coefficient of variation 9%) having an average grain size of 0.19 μm.

Then, the obtained emulsion was treated with the method described in JP-A-2-280139.
Desalted with the modified gelatin described in Japanese Patent Publication No. EA after desalination
The g was 190 mV at 50 ° C.

The desalted emulsion was adjusted to pH 5.58 and EAg123 mV.
After adjusting the temperature to 60 ° C, 1 mol of silver was added to chloroauric acid.
2.2 x 10^-FiveAfter adding the moles and stirring for 2 minutes, add sulfur to silver.
2.9 x 10 per mole^-6 Add mol and stir for an additional 38 minutes
Then, it was chemically aged. 4-per mol of silver at the end of ripening
Hydroxy-6-methyl-1,3,3a, 7-tetraza
7.5 x 10 inden^-3Mol, 1-phenyl-5-merca
3.5 × 10 Puttotetrazole^-Four28.4 mol and gelatin
g to give a silver halide emulsion A.

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of 100 μm thick polyethylene terephthalate film which had been subjected to the antistatic treatment described in Example 1 of JP-A-5-66512, the following composition was used. A silver halide emulsion layer coating solution was applied to form a silver halide emulsion layer. Further, a protective layer coating solution having the following composition was applied to the upper layer to form a protective layer. A backing layer coating liquid was applied on the other undercoat layer to form a backing layer. Further, a backing protective layer coating liquid was applied on the upper layer to form a backing protective layer, and a sample was obtained.

<< Silver Halide Emulsion Layer Coating Solution >> Silver Halide Emulsion A Silver amount 3.3 g / m ² Gelatin (including gelatin contained in Silver Halide Emulsion A) 71.5 g / m ²

[0148]

Embedded image Sodium-iso-amyl-n-decylsulfosuccinate 0.64 mg / m ² hydrazine derivative (shown in Table 1) 2.0 × 10 ^-4 mol / mol Ag Nucleation accelerator (shown in Table 1) 1.0 × 10 ^-3 mol / Mol Ag

<< Protective Layer Coating Liquid >> Sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Matting agent: Monodispersed silica with an average particle size of 3.5 μm 22 mg / m ² Hardener: 1,3-vinyl Sulfonyl-2-propanol 40 mg / m ²

[0150]

Embedded image Gelatin 1g / m ²

<< Backing Layer Coating Liquid >> Saponin 133 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 6 mg / m ² Colloidal silica 100 mg / m ² Gelatin 2.7 g / m ²

[0152]

Embedded image

[0153]

Embedded image

[0154]

Embedded image

[0155]

Embedded image

<< Backing Protective Layer Coating Liquid >> Matting Agent: Monodisperse Polymethyl Methacrylate with Average Particle Diameter 5.0 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Hardener: Glyoxal 5 mg / m ² gelatin 1 g / m ²

A He-N obtained by adhering a step wedge to the obtained sample and passing through an interference filter with a wavelength of 633 nm.
After performing high-intensity exposure for 10 ^-6 seconds using a light beam equivalent to a laser beam, an automatic processor for rapid processing (GR-26SR Konica Co., Ltd.) develops and fixes the following composition Was used under the following conditions. The replenishing amount of developer and fixer were each with ^{180cc / m 2, 280cc / m} 2, it was treated with Dry-to Dry 45 seconds.

<< Developer Formulation >> Sodium sulfite 55 g / liter Potassium carbonate 40 g / liter Hydroquinone 24 g / liter 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone (Dimezon S) 0.9 g / liter Potassium bromide 5 g / l 5-methyl-benzotriazole 0.13 g / l boric acid 2.2 g / l diethylene glycol 40 g / l

[0159]

Embedded image Water and potassium hydroxide are added to prepare a 1 liter solution having a pH of 10.5.

<< Fixing Solution Formulation >> Water 500 g Sodium thiosulfate 200 g Sodium sulfite (anhydrous) 20 g Ethylenediamine-4-acetic acid-2-sodium 0.1 g Tartaric acid 2 g Sodium hydroxide 0.25 g Aluminum miuban 0.10 mol / l Glutaraldehyde 0.20 mol / L Glacial acetic acid and sulfuric acid were added to adjust the pH to 4.8, and water was added to make 1 L.

<Development processing conditions> (Process) (Temperature) (Time) Development 35 ° C 30 seconds Fixing 33 ° C 20 seconds Washing with water Room temperature 20 seconds Drying 40 ° C 40 seconds

The optical density of the developed sample thus obtained was measured by PDA-
It was measured with a 65 (Konica Digital Densitometer), and the values of sensitivity, gamma, and black spot were calculated as follows. Table 1 shows the obtained results.
Shown in

The sensitivity was expressed as the reciprocal of the exposure amount required to give a density of 3.0, and was shown as a relative sensitivity when the sensitivity of Sample No. 1 was 100.

Gamma is the point at which the density of the characteristic curve is 0.1 and the density.
It is the gamma shown by the slope of a straight line connecting the 3.0 points.

A light-sensitive material having a gamma value of less than 6 has insufficient hardness and cannot be used as a light-sensitive material for printing. Even with a light-sensitive material having a gamma value of 6 or more and less than 10, the hardness is still insufficient and a super-high contrast image cannot be obtained. A light-sensitive material with a gamma value of 10 or more can obtain an ultra-high contrast image,
It is sufficiently practical as a photosensitive material for printing.

For black spots, the unexposed area was observed with a magnifying glass of 40 times, the occurrence of black spots was investigated, the average occurrence of black spots per field of view of the loupe was calculated, and evaluated according to the following evaluation criteria. did. Ranks 1 and 2 are levels that are not practically desirable.

<Evaluation Criteria> 5; 0 to 10 4; 10 to 25 to 3; 25 to 50 to 2; 50 to less than 100 1; 100 or more

[0168]

[Table 1]

[0169]

Embedded image

As is clear from Table 1, the samples according to the present invention exhibit high sensitivity and gamma, and prevent the generation of black spots, thus showing an excellent improving effect.

Example 2 A silver halide photographic light-sensitive material was prepared in the same manner as in Example 1 except that the hydrazine derivative and the nucleation accelerator were as shown in Table 2, and the same processing as in Example 1 was carried out. Relative sensitivity,
Gamma and black spots were evaluated. The obtained results are shown in Table 2.
Shown in

[0172]

[Table 2]

[0173]

Embedded image

As is clear from Table 2, the hydrazine derivative of the present invention exhibits high sensitivity and gamma even when two or more kinds thereof are used in combination, and the generation of black spots is prevented. Depending on the combination used,
It can be seen that an excellent improvement effect is exhibited without any problem.

Example 3 A silver halide photographic light-sensitive material was prepared in the same manner as in Example 1 except that the hydrazine derivative and the nucleation accelerator were as shown in Table 3, and the same processing as in Example 1 was carried out. Relative sensitivity,
Gamma and black spots were evaluated. The results obtained are shown in Table 3.
Shown in

For reference, Table 3 also shows the data of Samples 1 to 4 described in Example 1.

[0177]

[Table 3]

As is clear from Table 3, the samples according to the present invention exhibit high sensitivity and gamma, and prevent the generation of black spots, thus exhibiting an excellent improving effect.

Example 4 A silver halide photographic light-sensitive material was prepared in the same manner as in Example 1 except that the hydrazine derivative and the nucleation accelerator were as described in Table 4, and the processing was carried out in the same manner as in Example 1. Relative sensitivity,
Gamma and black spots were evaluated. Table 4 shows the results obtained.
Shown in

[0180]

[Table 4]

As is clear from Table 4, the hydrazine derivative of the present invention exhibits high sensitivity and gamma even when two or more kinds thereof are used in combination, and the generation of black spots is prevented. Depending on the combination used,
It can be seen that an excellent improvement effect is exhibited without any problem.

[0182]

The silver halide photographic light-sensitive material of the present invention comprises:
High contrast can be provided by using a stable developer, excellent sharpness, excellent dot quality, high activity, photographic quality is not impaired by black spots, etc. There is little fluctuation and there is no adverse impact on the environment. Further, even if the development process using a developer having a pH of 11.0 or less, or even when processed with a developer capable of rapid processing, high contrast is obtained, and in the running process of the silver halide photographic light-sensitive material, A stable photographic image can be provided even if the replenishment amount of the developer is small.

The hydrazine compound used in the silver halide photographic light-sensitive material of the present invention is easy to synthesize and excellent in safety.

Continuation of the front page (72) Inventor, Otowa Komamura, No. 1 Sakuramachi, Hino City, Tokyo Konica Stock Company

Claims (9)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer, which contains at least one compound represented by the following general formula (A1). material. Embedded image [Wherein R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, A represents a divalent linking group, and B represents a reaction with an oxidized product of a developing agent during development under alkaline conditions. NHN
It represents a group that is cleaved from H-. R ₁ , R ₂ , R ₃ , A and B
Each group represented by may have a substituent.
R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. ] 2. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (A1) is a compound represented by the following general formula (A2). Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, and B represents a group which is cleaved from —NHNH— by a reaction with an oxidized product of a developing agent during development under alkaline conditions. Each group represented by R ₁ , R ₂ , R ₃ and B may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. L, L ₁ and L ₂ represent an alkylene group, an arylene group or a divalent heterocyclic group,
J ₁ and J ₂ are —CO—, —SO ₂ —, —O—, —S—,
-CONH -, - NHCO -, - SO 2 NH -, - NH
_{SO 2 -, - NHCONH -,} - OCO -, - COO
-, -OCONH-, -NHCOO-, -NHCSNH
-, - it represents a NHSO ₂ NH-. k represents an integer of 0 or 1, m and n represent an integer of 0 to 4, and m or n is 2
In the above case, L ₁ and L ₂ , and J ₁ and J ₂ may be the same or different. ] 3. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (A1) is a compound represented by the following general formula (A3). Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, and A represents a divalent linking group. R ₁ , R ₂ , R
Each group represented by ₃ and A may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. G is -CO -, - COCO -, - SO 2
-, - SO -, - POR 4 -, represents an iminomethylene group, R ₄ represents an alkoxy group or an aryloxy group. D is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, -NR ₆ R _7, represent -OR _8, R ₆ and R ₇ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a cycloalkyl group R ₈ represents an alkyl group, an aryl group, a heterocyclic group, or a cycloalkyl group. D may also contain a moiety that causes a cyclization reaction that splits the -GD moiety from the rest of the molecule to produce a cyclic structure containing the atoms of the -GD moiety. -G-D as a whole, under alkaline conditions,
It is a group that is cleaved from —NHNH— by a reaction with an oxidized product of a developing agent during development. ] 4. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (A1) is a compound represented by the following general formula (A4). Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, and R ₃ represents an alkylene group. Each group represented by R ₁ , R ₂ and R ₃ may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. L ₀ , L ₁ and L
₂ represents an alkylene group, an arylene group or a divalent heterocyclic group, and J ₁ and J ₂ are —CO—, —SO ₂ —, —O—, —
S -, - CONH -, - NHCO -, - SO 2 NH-,
_{-NHSO 2 -, - NHCONH -,} - OCO -, - C
OO-, -OCONH-, -NHCOO-, -NHCS
NH -, - represents a NHSO ₂ NH-. k represents an integer of 0 or 1, m and n represent an integer of 0-4. When m or n is 2 or more, L ₁ and L ₂ , and J ₁ and J ₂ may be the same or different. E represents a saturated heterocyclic group, and R ₅ represents a hydrogen atom or a group capable of substituting for a benzene ring. ] 5. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (A1) is a compound represented by the following general formula (A5). Embedded image [In the formula, R ₁ and R ₂ represent an alkyl group, R ₃ represents an alkylene group, and A represents a divalent linking group. R ₁ , R ₂ , R
Each group represented by ₃ and A may have a substituent. R ₁ and R ₂ or R ₂ and R ₃ may combine to form a ring. G is -CO -, - COCO -, - SO 2
-, - SO -, - POR 4 -, represents an iminomethylene group, R ₄ represents an alkoxy group or an aryloxy group. Y represents a non-metal atomic group forming a 5- or 6-membered ring. R _a , R _b , R _c and R _d are a hydrogen atom, an alkyl group,
Represents an aryl group or an alkenyl group, Z is a group which, under alkaline conditions, undergoes a nucleophilic attack on -G- following the reaction with an oxidized product of a developing agent, causing splitting from the residual molecule, and causing a cyclization reaction with G. Represents p and q represent an integer of 0 or 1, and R _a , R _b , R _c , R _d , p and q may be the same or different. ] 6. At least one silver halide emulsion layer
The silver halide photographic light-sensitive material having the following general formula
Contain at least one compound represented by (B1)
A silver halide photographic light-sensitive material, characterized in that: Embedded image[Wherein, R _{twenty one}Is an alkyl group, aryl group, or heterocyclic group
Represents, R_{twenty two}Represents a hydrogen atom, an alkyl group, or an aryl group.
You. X_TwoRepresents a hydrogen atom or a group capable of substituting on the thiophene ring.
You. ] 7. The silver halide photographic light-sensitive material according to claim 6, wherein the compound represented by the general formula (B1) is a compound represented by the following general formula (B2). Embedded image [In the formula, R ₂₂ represents a hydrogen atom, an alkyl group or an aryl group, and R ₂₃ represents a hydrogen atom or a monovalent group. X ₂ represents a hydrogen atom or a group capable of substituting for the thiophene ring. L ₂₁ and L ₂₂
Represents an alkylene group, an arylene group or a divalent heterocyclic group, and J ₂₁ and J ₂₂ are —CO—, —SO ₂ —, —O—, —.
S-, -CONH-, -NHCO-, -NHCONH
-, -OCO-, -COO-, -OCONH-, -NH
COO -, - NHCSNH -, - representing the NHSO ₂ NH-. Y ₂ represents a hydrogen atom or a group capable of substituting on the benzene ring. k2 represents an integer of 0 or 1, m2 and n2 are 0 to 4
When m2 or n2 is 2 or more, L ₂₁ and L ₂₂ , J ₂₁ and J ₂₂ may be the same or different. ] 8. The silver halide photographic light-sensitive material according to claim 6, wherein the compound represented by the general formula (B1) is a compound represented by the following general formula (B3). Embedded image [In the formula, R ₂₃ represents a hydrogen atom or a monovalent group. X ₂ represents a hydrogen atom or a group capable of substituting for the thiophene ring. L ₂₁ and L ₂₂ represent an alkylene group, an arylene group or a divalent heterocyclic group, and J ₂₁ and J ₂₂ represent —CO—, —SO ₂ —, —O.
-, -S-, -CONH-, -NHCO-, -NHCO
NH-, -OCO-, -COO-, -OCONH-,-
NHCOO -, - NHCSNH -, - NHSO 2 NH-
Represents Y ₂ represents a hydrogen atom or a group capable of substituting on the benzene ring. k2 represents an integer of 0 or 1, m2 and n2 are 0 to
Represents an integer of 4, and when m2 or n2 is 2 or more, L ₂₁ and L ₂₂ , J ₂₁ and J ₂₂ may be the same or different. ] 9. A silver halide photographic light-sensitive material is prepared by the following general method.
Formula (A1) -general formula (A5) or general formula (B1) -one
PH 11.0 or less in the presence of the compound represented by the general formula (B3)
Silver halide photography characterized by being developed with other developing agents
Method of developing photosensitive material. Embedded image[Wherein, R₁And R_TwoRepresents an alkyl group;_ThreeIs archi
Represents a len group, A represents a divalent linking group, B represents an alkali
-NHN by reaction with oxidized form of developing agent
It represents a group that is cleaved from H-. R₁, R_Two, R_Three, A and B
Each group represented by may have a substituent.
Also, R₁And R_TwoOr R_TwoAnd R_ThreeAre bound together to form a ring
Good. ] [Chemical formula 10][Wherein, R₁And R_TwoRepresents an alkyl group;_ThreeIs archi
Represents a len group, and B is the main developer during development under alkaline conditions.
Shows groups that are cleaved from -NHNH- by reaction with drug oxidants.
You. R₁, R_Two, R_ThreeAnd the groups represented by B are
It may have a substituent. Also, R₁And R_TwoOr R_TwoWhen
R_ThreeMay combine with each other to form a ring. L, L₁And L_TwoIs
A alkylene group, an arylene group, a divalent heterocyclic group,
J₁And J_TwoIs -CO-, -SO_Two-, -O-, -S-,
-CONH-, -NHCO-, -SO_TwoNH-, -NH
SO_Two-, -NHCONH-, -OCO-, -COO
-, -OCONH-, -NHCOO-, -NHCSNH
-, -NHSO_TwoRepresents NH-. k is an integer of 0 or 1
, M and n represent an integer of 0 to 4, and m or n is 2
When above, L₁And L_Two, J₁And J_TwoAre the same
Or they may be different. ] [Chemical 11][Wherein, R₁And R_TwoRepresents an alkyl group;_ThreeIs archi
Represents a len group, and A represents a divalent linking group. R₁, R_Two, R
_ThreeAnd each group represented by A has a substituent,
Is also good. Also, R₁And R_TwoOr R_TwoAnd R_ThreeCombine to form a ring
May be done. G is -CO-, -COCO-, -SO_Two
-, -SO-, -POR_Four-, Represents an iminomethylene group
Then R_FourRepresents an alkoxy group or an aryloxy group
You. D is a hydrogen atom, an alkyl group, an aryl group, a heterocycle
Group, -NR₆R₇, -OR₈Represents R₆And R₇Is hydrogen field
Child, alkyl group, aryl group, heterocyclic group, cycloal
Represents a kill group;₈Represents an alkyl group, an aryl group,
It represents a cyclic group or a cycloalkyl group. Also, D is the -GD section
Splitting the fraction from the rest of the molecule, including the atoms in the -GD portion
Contains a moiety that undergoes a cyclization reaction that produces a cyclic structure
May be. -G-D as a whole, under alkaline conditions,
Opened from -NHNH- by reaction with oxidized form of developing agent during development.
A group that cleaves. ] [Chemical formula 12][Wherein, R₁And R_TwoRepresents an alkyl group;_ThreeIs archi
Represents a len group. R₁, R_TwoAnd R_ThreeEach group represented by
Each may have a substituent. Also, R₁And R_TwoOr
R_TwoAnd R_ThreeMay combine with each other to form a ring. L₀, L₁And L
_TwoIs an alkylene group, an arylene group or a divalent heterocyclic group
Represents, J₁And J_TwoIs -CO-, -SO_Two-, -O-,-
S-, -CONH-, -NHCO-, -SO_TwoNH-,
-NHSO_Two-, -NHCONH-, -OCO-, -C
OO-, -OCONH-, -NHCOO-, -NHCS
NH-, -NHSO_TwoRepresents NH-. k is 0 or 1
Represents an integer, and m and n represent an integer of 0-4. Also, m
Or when n is 2 or more, L₁And L_Two, J₁And J_TwoEach
These may be the same or different. E is saturated hetero
The ring group is R_FiveCan be replaced by hydrogen atom or benzene ring
Represents a group. ] [Chemical 13][Wherein, R₁And R_TwoRepresents an alkyl group;_ThreeIs archi
Represents a len group, and A represents a divalent linking group. R₁, R_Two, R
_ThreeAnd each group represented by A has a substituent,
Is also good. Also, R₁And R_TwoOr R_TwoAnd R_ThreeCombine to form a ring
May be done. G is -CO-, -COCO-, -SO_Two
-, -SO-, -POR_Four-, Represents an iminomethylene group
Then R_FourRepresents an alkoxy group or an aryloxy group
You. Y is a non-metallic atomic group forming a 5- or 6-membered ring
Represent. R_a, R_b, R_cAnd R_dRepresents a hydrogen atom, an alkyl group,
Represents an aryl group or an alkenyl group, Z is an alkaline condition
Below, during development, the reaction with the oxidized product of the developing agent is followed by -G-
Performs a nucleophilic attack, splits from the rest of the molecule, and cyclizes with G
Represents a group that causes a reaction. p and q are integers of 0 or 1
Represents R_a, R_b, R_c, R_d, P and q are the same
Or may be different. ] [Chemical 14][Wherein, R _{twenty one}Is an alkyl group, aryl group, or heterocyclic group
Represents, R_{twenty two}Represents a hydrogen atom, an alkyl group, or an aryl group.
You. X_TwoRepresents a hydrogen atom or a group capable of substituting on the thiophene ring.
You. ] [Chemical 15][Wherein, R_{twenty two}Represents a hydrogen atom, an alkyl group, or an aryl group.
Then R_{twenty three}Represents a hydrogen atom or a monovalent group. X_TwoIs hydrogen field
And a group capable of substituting for the thiophene ring. L_{twenty one}, L_{twenty two}Is
Represents an alkylene group, an arylene group, a divalent heterocyclic group
And J_{twenty one}And J_{twenty two}Is -CO-, -SO_Two-, -O-,-
S-, -CONH-, -NHCO-, -NHCONH
-, -OCO-, -COO-, -OCONH-, -NH
COO-, -NHCSNH-, -NHSO_TwoShow NH-
You. Y_TwoRepresents a hydrogen atom or a group capable of substituting on the benzene ring.
You. k2 represents an integer of 0 or 1, m2 and n2 are 0 to 4
Represents an integer, and when m2 or n2 is 2 or more, L_{twenty one}as well as
L_{twenty two}, J_{twenty one}And J_{twenty two}Are the same but different
May be. ] [Chemical 16][Wherein, R_{twenty three}Represents a hydrogen atom or a monovalent group. X_TwoIs water
It represents a group capable of substituting an elementary atom or a thiophene ring. L_{twenty one}, L
_{twenty two}Is an alkylene group, an arylene group or a divalent heterocyclic group
Represents, J_{twenty one}And J_{twenty two}Is -CO-, -SO_Two-, -O-,
-S-, -CONH-, -NHCO-, -NHCONH
-, -OCO-, -COO-, -OCONH-, -NH
COO-, -NHCSNH-, -NHSO_TwoShow NH-
You. Y_TwoRepresents a hydrogen atom or a group capable of substituting on the benzene ring.
You. k2 represents an integer of 0 or 1, m2 and n2 are 0 to 4
Represents an integer, and when m2 or n2 is 2 or more, L_{twenty one}as well as
L_{twenty two}, J_{twenty one}And J_{twenty two}Are the same but different
May be. ]