JP2003029367A - Silver halide photographic sensitive material and hydroxylamine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in pressure resistance, sensitivity and against fog of an objective layer by using an immobilized compound having suppressed diffusibility. SOLUTION: The silver halide photographic sensitive material contains at least one of new hydroxylamine compounds of formulae (1)-(6). Such hydroxylamine compounds are provided.

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 excellent in pressure resistance, sensitivity and fog.

[0002]

2. Description of the Related Art Generally, various pressures are applied to a silver halide photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material) coated with a silver halide emulsion. For example, a sheet-shaped film such as a printing photosensitive material or a direct medical X-ray sensitive material is often bent or bent because a person directly handles it. When various pressures are applied to the light-sensitive material in this way, the pressure is applied to the silver halide grains by using gelatin as a binder of silver halide grains or a plastic film as a support medium. When pressure is applied to the silver halide grains, the photographic performance of the light-sensitive material changes. For example, K. B. Mother; J. Opt. Soc. A
m. 38, 1054, (1948), P .; Faele
ns and P.N. de Smet; Sci. et
Ind. Photo. 25, No. 5,178 (195
4), P. Falenens; J. Photo. Sci. ;
2, 105 (1954) and the like.

On the other hand, the image quality of the photosensitive material, that is, color reproducibility
Sharpness and graininess have made remarkable progress. However, the demands on the image quality of the light-sensitive material are still constant, and further progress is required. For this reason, various emulsion techniques and coupler techniques have been studied and each has produced great results. However, among these techniques, there are many cases in which fog rises, and a countermeasure technique therefor has long been desired.

Further, in order to make up for the drawback, a method of adding various additives to the emulsion has been taken. However, when a diffusible compound is used, it diffuses to a layer other than the layer to be corrected, and other layers. However, there is a problem in that the photographic performance is impaired, for example, the sensitivity is reduced. Therefore, there has been a demand for a technique for preventing the increase of fog in a target layer without impairing the photographic performance of other layers.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide a silver halide photographic light-sensitive material excellent in pressure resistance, sensitivity and fog of a target layer by using an immobilized compound with suppressed diffusivity. To provide.

[0006]

The above objects of the present invention have been achieved by the following constitutions.

1. A silver halide photographic light-sensitive material comprising at least one compound represented by the above general formula (1).

2. The above general formula (2) or general formula (3)
A silver halide photographic light-sensitive material containing at least one compound represented by:

3. A silver halide photographic light-sensitive material containing at least one of the compounds represented by the general formula (4).

4. A silver halide photographic light-sensitive material characterized in that in the general formula (4), R ₄₂ is a substituted or unsubstituted hydroxylamino group.

5. A silver halide photographic light-sensitive material comprising at least one compound represented by the general formula (5).

6. A silver halide photographic light-sensitive material comprising at least one polymer containing a unit formed of the structure represented by the general formula (6).

7. A compound represented by the above general formula (1). 8. A compound represented by the above general formula (4).

9. A compound represented by the above general formula (5). 10. A compound represented by the above general formula (6).

11. A polymer compound formed from a structural unit represented by the above general formula (6).

The present invention will be described in more detail. In the general formula (1), R ₁ is a hydrogen atom, an alkyl group (eg, methyl, ethyl, isopropyl, hexyl, hydroxylethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl, etc.), a cycloalkyl group (eg, cyclopropyl, cyclohexyl, etc.). ), An aryl group (eg, phenyl, naphthyl, p-methoxyphenyl, etc.), a heterocyclic group (eg, a pyrrolidine ring, a piperidine ring, an aziridine ring, an azetidine ring, a morpholine ring, an imidazolidine ring,
Pyrazolidine ring, piperazine ring, oxirane ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, thiazolidine ring, oxazolidone ring, piperidone ring, pyrrolidone ring, succinimide derivative, succinic anhydride derivative, sulfolane ring, pyridine ring, pyrimidine ring, furan Ring, pyrrole ring, quinoline ring, etc.) and the like.

W ₁ represents a silver affinity group or a dye residue. The silver affinity group is a group derived from a cyclic or chain thioether (eg, dimethyl sulfide, methyl ethyl sulfide, methyl phenyl sulfide, Groups derived from thiocrown ethers), groups derived from aliphatic mercaptans (eg, groups derived from methyl mercaptan, propyl mercaptan, etc.), aromatic mercaptans (eg, thiophenol,
A group derived from thionaphthol), a group derived from a cyclic or chain thioamide, a group derived from a cyclic or chain thioureido, a group derived from a heterocyclic mercaptan (a carbon to which an —SH group is bonded) When a nitrogen atom is next to the atom, it is synonymous with a cyclic thioamide group having a tautomeric relationship with this, and specific examples of this group are the same as those listed below), imide silver-forming azole And a group derived from a nitrogen-containing aromatic ring quaternary salt (for example, a group derived from an N-methylpyridinium salt, an N-ethylquinolium salt, etc.) and the like, preferably thioamide and thioureido. , An aromatic mercaptan, a heterocyclic mercaptan, or a group derived from an azole capable of forming an imide silver, and more preferably a heterocyclic mercaptan or Is a group derived from a bromide silver formable azole. Specific examples of the group derived from a heterocyclic mercaptan and the group derived from an azole capable of forming imide silver include mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,
3,4-oxadiazole, 2-mercapto-1,3
4-thiadiazole, 2-mercaptoimidazole, 2
-Mercapto-1,3-oxazole, 2-mercapto-1,3-thiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptopyridine, 2-
Mercaptopyrimidine, a group derived from a heterocyclic mercaptan such as mercaptotriazine, benzotriazole, triazole, tetrazole, indazole,
Examples thereof include groups derived from imide-silver forming azoles such as benzimidazole, imidazole, tetrazaindene, indazole, and purine. Among these, preferred are mercaptotetrazole and 3-mercapto-.
1,2,4-triazole, 2-mercapto 1,3,4
-Oxadiazole, 2-mercapto-1,3,4-thiadiazole, 2-mercaptobenzimidazole, 2
-Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptopyrimidine, mercaptotriazine, benzotriazole, a group derived from tetrazole, more preferably mercaptotetrazole, 3-mercapto-1,2,4-triazole,
A group derived from 2-mercapto-1,3,4-thiadiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, benzotriazole, and tetrazole, and more preferably mercaptotetrazole and 2-mercapto-1,3. It is a group derived from 4-thiadiazole and benzotriazole.

The dye residue is represented by the following general formula (7),
Examples include the group represented by (8) or (9). In formula (7), (8) or (9), Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are each a non-metal atom necessary for forming a 5- or 6-membered nitrogen-containing ring. Represents a group. Q ₁ , Q ₂ and Q ₃
Each represents a nonmetallic atomic group necessary for forming an acidic nucleus. M ₁ , M ₂ and M ₃ represent a charge neutralizing counterion,
n1, n2 and n3 represent an integer of 0 or more necessary for neutralizing the charge in the molecule. L ₁ , L ₂ , L ₃ , L ₄ , L
_{5, L 6, L 7,} L 8, L 9, L 20, L 21 and L ₂₂ each represents a methine group or a substituted methine group may form a ring with other methine groups Alternatively, it may form a ring with the auxochrome. u1, u2, u3, u4 and u5 each represent an integer of 0 or 1. s represents an integer of 0 to 4, r represents 0 or 1. t1 is an integer of 0 to 4, t
2 represents an integer of 0 to 3, but when r = 0 (t1 + t2)
Represents an integer of 0 <(t1 + t2) ≦ 6. v1 and v
Each 2 represents an integer of 0 to 2. R ₇₁ , R ₇₂ , R ₈ ,
Each of R ₉₁ and R ₉₂ represents an aliphatic group.

In the general formula (1), L ₁₁ represents a linking group, and the linking group is an atom or atomic group containing at least one of C, N, S and O. Specifically, for example, -O-, -S-, -N (R)-, -CO-, -SO.
_2- , an alkylene group (for example, methylene, ethylene,
1,4-cyclohexylene, dodecylene, hexadecylene, 2-ethylhexylene, 2-hexyldecalene, etc.), arylene groups (eg, phenylene, naphthylene, etc.), heterocyclic groups (eg, pyrrolidine ring, piperidine ring, aziridine ring) , Azetidine ring, morpholine ring, imidazolidine ring, pyrazolidine ring, piperazine ring, oxirane ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, thiazolidine ring, oxazolidone ring, piperidone ring, pyrrolidone ring,
Succinimide derivative, succinic anhydride derivative, sulfolane ring, pyridine ring, pyrimidine ring, triazine ring, furan ring, pyrrole ring, quinoline ring, etc.) or a combination thereof. These may be further substituted with a substituent. As the substituent, an alkyl group (eg, methyl, ethyl, etc.), an aryl group (eg, phenyl, naphthyl, etc.), an amino group, an alkylamino group (eg, methylamino, dimethylamino, etc.), an alkoxy group (eg, methoxy, ethoxy, etc.), Aryloxy group (eg phenyloxy etc.), acyl group (eg acetyl, benzoyl etc.), hydroxyl group, chlorine atom,
It represents a bromine atom, a fluorine atom, an iodine atom, a carbamoyl group (eg N-methylcarbamoyl etc.), a sulfonyl group (methanesulfonyl etc.), a sulfamoyl group (eg methylsulfamoyl etc.) and the like. These can be bonded to any position of the structure represented by the general formula (7), (8) or (9) and any substituent.

[0020]

[Chemical 5]

In the general formula (2), R ₂₁ is a hydrogen atom,
Alkyl groups (eg methyl, ethyl, isopropyl, hexyl, hydroxylethyl, stearyl, dodecyl,
Eicosyl, docosyl, oleyl etc.), cycloalkyl group (eg cyclopropyl, cyclohexyl etc.), aryl group (eg phenyl, naphthyl, p-methoxyphenyl etc.), heterocyclic group (eg pyrrolidine ring, piperidine ring, aziridine ring, azetidine) Ring, morpholine ring, imidazolidine ring, pyrazolidine ring, piperazine ring, oxirane ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, thiazolidine ring, oxazolidone ring, piperidone ring, pyrrolidone ring, succinimide derivative, succinic anhydride derivative, sulfolane Ring, a pyridine ring, a pyrimidine ring, a furan ring, a pyrrole ring, a quinoline ring, etc., and R ₂₂ is an alkyl group (for example, methyl,
Ethyl, isopropyl, hexyl, hydroxylethyl, stearyl, dodecyl, eicosyl, docosyl, oleyl etc.), cycloalkyl group (eg cyclopropyl, cyclohexyl etc.), aryl group (eg phenyl, naphthyl, p-methoxyphenyl etc.), amino group (Eg, methylamino, ethylamino, diethylamino, dihexylamino, etc.), alkoxy group (eg, methoxy, ethoxy, hexadecyloxy, etc.), aryloxy group (eg, phenyloxy, naphthoxy, etc.), heterocyclic group (eg, pyrrolidine ring) , Piperidine ring, aziridine ring, azetidine ring, morpholine ring, imidazolidine ring, pyrazolidine ring, piperazine ring, oxirane ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, thi Zolidine ring, oxazolidone ring, piperidone ring, pyrrolidone ring, succinimide derivative, succinic anhydride derivative, sulfolane ring, pyridine ring, pyrimidine ring, furan ring, pyrrole ring, quinoline ring, etc., and those hetero groups have substituents. A carboxamide group (eg, acetamide, ethaneamide, hexanamide, cyclohexanamide, succinamide, phenylamide, etc.), sulfonamide group (eg, methanesulfonamide, ethanesulfonamide, cyclohexanesulfonamide, benzenesulfonamide, etc.), Hydroxylamine, O-alkylhydroxylamino group (for example, O-ethylhydroxylamino, O-dodecylhydroxylamino, O-2-ethylhexylhydroxylamino, etc.), O-arylhydroxy Arylamino group (e.g., O- phenylhydroxylamine amino, O-2-methylphenyl hydroxylamino, etc.),
Hydrazino group (phenylhydrazino, acetohydrazino, benzoylhydrazino, p-toluenesulfonylhydrazino, etc.), acyl group (for example, acetyl, propionyl, myristyl, 3-tetradecyloxycarbonylpropionyl, benzoyl, p-dodecylaminobenzoyl, etc.), Alkyl or aryl sulfonyl groups (eg methane sulfonyl, octane sulfonyl, benzene sulfonyl, toluene sulfonyl etc.), alkyl or aryl sulfinyl groups (eg methane sulfinyl, benzene sulfinyl etc.), carbamoyl groups (eg N-
Ethylcarbamoyl, N-phenylcarbamoyl, N,
N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl, etc.), sulfamoyl group (for example, N-methylsulfamoyl, N, N-diethylsulfamoyl,
N-phenylsulfamoyl, N-cyclohexyl-N
-Phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl, etc.), aryloxycarbonyl group (For example, phenoxycarbonyl, naphthoxycarbonyl, etc.).

In the general formula (2), W ₂ and L ₁₂ have the same meanings as W ₁ and L ₁₁ in the general formula (1).

In the general formula (3), W ₃ has the same meaning as W ₁ in the general formula (1). R ₃ has the same meaning as R ₁ in formula (1).

In the general formula (4), R ₄₁ has the same meaning as R ₁ in the general formula (1). R ₄₂ is the general formula (2)
Is synonymous with R _{22 in} . X is a heterocyclic group (eg,
Pyrrolidine ring, piperidine ring, aziridine ring, azetidine ring, morpholine ring, imidazolidine ring, pyrazolidine ring, piperazine ring, oxirane ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, thiazolidine ring, oxazolidone ring, piperidone ring, pyrrolidone ring , Succinimide derivative, succinic anhydride derivative, sulfolane ring, pyridine ring, pyrimidine ring,
Furan ring, pyrrole ring, quinoline ring, etc.), and Y represents a substituent. As the substituent, an alkyl group (for example, hexyl, oleyloxymethyl, dodecyloxycarbonylmethyl, hexadecyloxyethyl, octyl, hexadecyl, 2-ethylhexyl, 2-hexadecyl, stearyl, docosyl, etc.), an aryl group (phenyl, p-
Tetradecanyloxyphenyl, naphthyl etc.), alkyloxycarbonyl group (eg octyloxycarbonyl, stearyloxycarbonyl etc.), aryloxycarbonyl group (eg phenyloxycarbonyl, naphthyloxycarbonyl etc.), alkylamino group (2-
Hexadecylamino, dihexylamino, etc.), arylamino (phenylamino, diphenylamino, etc.), alkylthio group (ethylthio, hexylthio, etc.), arylthio group (eg, phenylthio, p-tetradecanyloxyphenylthio, etc.), acyl group (eg, Acetyl, benzoyl, etc.), carboxamide (eg, acetamide, hexanamide, phenylamide, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), alkyl or arylsulfonyl group (eg, octanesulfonyl, toluenesulfonyl, etc.), carbamoyl Group (eg N-ethylcarbamoyl, N-phenylcarbamoyl etc.), sulfamoyl group (eg N-methylsulfamoyl, N-ethyl-N-dodecylsulfamoyl etc.) Hexyl group (methoxy, hexadecyloxy, etc.) aryloxy groups (phenyloxy, Nafutookishi etc.) representing the like.

In the general formula (5), R ₅₁ has the same meaning as R ₁ in the general formula (1). W ₅ and L ₁₅ have the same meanings as W ₁ and L ₁₁ in the general formula (1). J represents a linking group, and examples thereof include a linking group having the same meaning as L ₁₁ in formula (1).

In the general formula (6), R ₆ has the same meaning as R ₁ in the general formula (1). P represents a polymerizable group containing an ethylenically unsaturated functional group, and specifically, a substituent derived from an unsaturated carboxylic acid such as a methacryloyloxy group, an acryloyloxy group or a crotonoyloxy group, a vinylbenzyloxy group, a vinyloxy group. Group, vinyloxycarbonyl group and the like.

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this. However, (79) to (89) represent the structure of the monomer.

[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

The synthesis examples of the compound of the present invention are shown below. Synthesis example 1

[0040]

[Chemical 17]

First, 10.0 g of glutaric anhydride (0.0
877 mol) and 3-amino-benzotriazole 1
1.8 g (0.0877 mol) was mixed and stirred at 120 ° C. for 5 hours. After the reaction is completed, the mixture is allowed to cool and ethyl acetate 10m
l was added and stirred, and when the crystals were sufficiently extracted, the crystals were filtered and washed. 15.2 g of white crystals (11-1) (yield 70
%)Obtained. Next, 10g of (11-1) (0.04mo
l) is dissolved in 50 ml of dichloromethane and DMF 0.2 is added.
After adding ml, 6.1 g of oxalyl chloride (0.
(048 mol) was added and stirred for 1 hour. N for the end of reaction
After confirming the MR spectrum, the solvent was removed under reduced pressure. 50% hydroxylamine aqueous solution in a separate container beforehand 2.
5 g (0.0372 mol) was dissolved in 30 ml of water, 3.36 g (0.04 mol) of sodium hydrogencarbonate and 50 ml of ethyl acetate were added to the solution which had been stirred, and the above residue was dissolved in 50 ml of ethyl acetate. The solution was added dropwise while keeping at -10 ° C. Then, it returned to room temperature and was made to react for 2 hours. After the reaction was completed, the temperature of the reaction liquid was raised to 50 ° C. to perform liquid separation. The organic layer was washed twice with water and dried over magnesium sulfate. After filtration and removal of the solvent under reduced pressure, the residue was purified by silica gel column chromatography (EA / toluene = 1/1) to obtain 6.4 g (yield 65%) of compound (11). The structure was confirmed by NMR spectrum and MASS spectrum.

Synthesis Example 2

[0043]

[Chemical 18]

First, 13.6 g of cyanuric chloride
(0.074 mol) 130 ml of acetone and 13 m of water
It was dissolved in a mixed solution of 1 and cooled to 10 ° C or lower. 10 g (0.074 mol) of adenine was dissolved in water in a separate device, and 2.96 g (0.074 mol) of sodium hydroxide was added to complete dissolution. This adenine solution was added to the above acetone solution 1
The solution was added dropwise while keeping the temperature below 0 ° C. Stirring was continued for 1 hour as it was, and when the reaction was completed, 260 ml of water was added to suspend the reaction and further stirred for 30 minutes. The suspension was filtered, washed with water, and then dried to obtain 17.8 g (yield 85%) of white crystals (36-1). Next, 15.0 g of (36-1) (0.0
530 mol) was suspended in 75 ml of THF, 35 g (0.53 mol) of 50% hydroxylamine aqueous solution was added, and the mixture was stirred at 60 ° C. for 3 hours. After the reaction was completed, the aqueous layer was removed, the organic layer was dried over magnesium sulfate, and the solvent was removed under reduced pressure. The residue was recrystallized by adding 45 ml of iso-propyl alcohol. When fully crystallized, it was filtered to obtain 11.4 g (yield 78%) of white crystals (36). The structure was confirmed by NMR spectrum and Mass spectrum.

Synthesis Example 3

[0046]

[Chemical 19]

First, 8.5 g of (42-1) (0.01
305 mol) in 100 ml of dichloromethane,
1.7 g (0.014) of thionyl chloride with stirring at room temperature
36 mol) was added dropwise. After confirming the completion of the reaction by NMR spectrum, the solvent was removed under reduced pressure. 50 in another container in advance
% Hydroxylamine aqueous solution 0.8 g (0.0121 m
ol) is dissolved in 20 ml of water, and sodium hydrogen carbonate 1.
To the solution, to which 02 g (0.0121 mol) and 40 ml of ethyl acetate had been added and stirred, was added the above residue to ethyl acetate (3).
It was dissolved in 0 ml and added dropwise while maintaining 5 to 10 ° C. Then, it returned to room temperature and was made to react for 2 hours. After the reaction was completed, the temperature of the reaction liquid was raised to 50 ° C. to perform liquid separation. The organic layer was washed twice with water and dried over magnesium sulfate. After filtration and removal of the solvent under reduced pressure, the residue was purified by silica gel column chromatography (MeOH / toluene = 1/1) to give compound (4
5.0 g (yield 62%) of 2) was obtained. Structure is NMR
It was confirmed by spectrum and MASS spectrum.

Synthesis Example 4

[0049]

[Chemical 20]

5 g of cyanuric chloride (0.0271 m
ol) was suspended in a mixed solution of 20 ml of acetone and 7 ml of water. 8.4 g of (55-1) (0.0
271 mol) was added dropwise. After completion of dropping, the mixture was stirred at 5 to 10 ° C for 1 hour, and then stirred for 1 hour while spontaneously heating to 25 ° C. The mixed solution was dissolved by heating at 40 ° C. to homogenize it, and the mixed solution was poured into 100 ml of ice-cooled 1 mol / liter HCl solution under stirring and stirring was continued for another 30 minutes. The precipitate was filtered, washed with 20 ml of water, and dried at room temperature to obtain 13.9 g of crude crystals. 28 ml of ethyl acetate was added to 13.9 g of the crude crystals, and the mixture was suspended at 40 ° C. and stirred for 10 minutes, then allowed to cool to room temperature with stirring and stirred for 5 hours. Filter and dry (55-
10.0 g (yield 69.4%) of 2) was obtained. Then (55
-2) of 3.8 g was suspended in 15 ml of THF, 6 ml of 50% aqueous solution of hydroxylamine was added dropwise, and the internal temperature was 60 ° C.
The temperature was raised to. As the temperature increased, it became uniform. About 4
After stirring for an hour, the mixture was allowed to cool, 10 ml of saturated brine was added, the aqueous layer was separated and removed, and magnesium sulfate was added to the THF layer.
After filtration, the solvent was removed under reduced pressure. 7m ethyl acetate on the residue
1 was added and dissolved, and the mixture was poured into 28 ml of acetonitrile and crystallized. After stirring for 30 minutes, it was filtered, washed with 14 ml of acetonitrile and dried. 3.0 g of (55)
(Yield 93%) was obtained.

Synthesis Example 5

[0052]

[Chemical 21]

5g of (75-1) (0.0161mo
l) was suspended in a mixed solution of 20 ml of acetone and 7 ml of water. 1.6 g of (75-2) (0.00
805 mol) was added dropwise. After completion of dropping, the mixture was stirred at 5 to 10 ° C for 1 hour, and then stirred for 1 hour while spontaneously heating to 25 ° C. The mixed solution was dissolved by heating at 40 ° C. to homogenize it, and the mixed solution was poured into 100 ml of ice-cooled 1 mol / liter HCl solution under stirring and stirring was continued for another 30 minutes. The precipitate was filtered, washed with 20 ml of water, and dried at room temperature to obtain 6.1 g of crude crystals. 12 ml of ethyl acetate was added to 6.1 g of the crude crystals, and the suspension was suspended at 40 ° C. and stirred for 10 minutes, and then allowed to cool to room temperature with stirring and stirred for 5 hours. Filter and dry (75-3)
Was obtained 3.24 g (yield 54%). Next, 3.2 g of (75-3) was suspended in 15 ml of THF, 6 ml of a 50% aqueous solution of hydroxylamine was added dropwise, and the internal temperature was raised to 60 ° C. As the temperature increased, it became uniform. After stirring for about 4 hours, the mixture was allowed to cool, 10 ml of saturated brine was added, the aqueous layer was separated and removed, magnesium sulfate was added to the THF layer, and the solvent was removed under reduced pressure. 7 ml of ethyl acetate was added to the residue to dissolve it, and the mixture was poured into 28 ml of acetonitrile for crystallization. After stirring for 30 minutes, it is filtered and acetonitrile 14 m
It was washed with 1 and dried. 2.8 g of (75) (yield 8
9%) was obtained. The structure was confirmed by NMR spectrum and MASS spectrum.

Synthesis Example 6 To 50 ml of tetrahydrofuran, 4.0 g of (84) and 6.0 g of methyl methacrylate were added, and then 30 ml of tetrahydrofuran in which 0.93 g of azoisobutyronitrile was dissolved was added. Polymerization was carried out at 70 ° C. for 9 hours in a nitrogen atmosphere. After the tetrahydrofuran was distilled off under reduced pressure, 30
It was redissolved in ml of tetrahydrofuran and added dropwise to a large excess of methanol. The deposited precipitate was collected by filtration and vacuum dried at 40 ° C. 9.4 g of an off-white powdery polymer was obtained. This product was confirmed to have a weight average molecular weight of 8900 by GPC analysis using standard polystyrene as a reference. Also N
From the MR spectrum and UV spectrum, it was confirmed that the polymer was a copolymer of (84) and methyl methacrylate. The composition of the polymer was about (84): methyl methacrylate = 40: 70.

In the present invention, the general formulas (1) to
The compound represented by (4) is described in J. Org. Chem. , 2
7, 4054 (1962), J. Amer. Chem.
Soc. , 73, 2981 (1951), Japanese Patent Publication No. 49-
It can also be easily synthesized by the method described in 10692 or the like or a method analogous thereto.

In the present invention, the addition amount of the compounds represented by the general formulas (1) to (6) is not particularly limited, but when it is added to the light-sensitive silver halide emulsion layer, it is based on 1 mol of Ag of the addition layer. The range of 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻¹ mol is preferable, and the range of 1.0 × 10 ^{−3 to} 5.0 × 10 ⁻² mol is more preferable. 1 × when added to the non-photosensitive layer
10 ^{−6 to} 3 × 10 ⁻⁴ mol / m ² is preferable, and 1 × 10
^-5 to 1 × 10 ^-4 mol / m ² is more preferable.

In the present invention, the compounds represented by the general formulas (1) to (6) are dissolved in water, a water-soluble solvent such as methanol or ethanol, a hydrophobic solvent such as ethyl acetate or a mixed solvent thereof. It may be added or may be added by emulsion dispersion. When it dissolves in water, if the pH is higher or lower, the solubility increases.
May be added at high or low levels and dissolved.
In the present invention, two or more kinds of the compounds represented by the general formulas (1) to (6) may be used in combination.

In the present invention, the compounds represented by the general formulas (1) to (6) are not limited in addition, and may be added to the emulsion at any time.

The silver halide grains contained in the silver halide photographic emulsion relating to the present invention may have a regular crystal structure such as a cube, octahedron or tetradecahedron, or may have a spherical or plate shape. It may have an irregular crystal form. In these particles, any ratio of (100) plane to (111) plane can be used. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed.

In the present invention, the average grain size of silver halide grains is preferably 0.2 to 10 μm, and 0.3 to 7.0 μm.
Is more preferable, and 0.4 to 5.0 μm is most preferable.

In the present invention, any silver halide photographic emulsion such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used, but a monodisperse emulsion is preferred.

In the present invention, as the silver halide photographic emulsion, any silver halide such as silver iodobromide, silver iodochlorobromide, silver iodochloride and the like used for ordinary silver halide can be used. However, silver iodobromide and silver iodochlorobromide are particularly preferable.

In the present invention, the average silver iodide content of silver halide grains contained in the silver halide photographic emulsion is 1 to 4
It is preferably 0 mol%, more preferably 2 to 2
It is 0 mol%.

Core / shell type grains can be preferably used as the silver halide grains contained in the silver halide photographic emulsion of the present invention. The core / shell type particles are particles composed of a core and a shell coating the core,
The shell is formed by one or more layers. It is preferable that the core and the shell have different silver iodide contents.

Various methods well known in the art can be used for producing the silver halide photographic emulsion of the present invention. That is, a single jet method, a double jet method, a triple jet method, a silver halide fine grain supply method and the like can be used in any combination. Also, the pH in the liquid phase in which silver halide is produced,
A method of controlling pAg according to the growth rate of silver halide can also be used together.

A seed emulsion may be used in the production of the silver halide photographic emulsion of the present invention. When a seed emulsion is used, the silver halide grains in the seed emulsion may have a regular crystal structure such as a cube, octahedron or tetradecahedron, or may have a spherical or tabular shape. It may have an irregular crystal form. In these particles, (100) plane and (11) plane
1) Any surface ratio can be used. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed. In the present invention, when tabular silver halide grains are used, it is preferable that the silver halide grains in the seed emulsion used are twin crystal silver halide grains having twin planes. Twinned silver halide grains having twin planes are particularly preferred.

In the present invention, regardless of whether a seed emulsion is used or a seed emulsion is not used, as a condition for silver halide nucleation and ripening, a method known in the art is applied. You can

In the production of the silver halide photographic emulsion of the present invention, a silver halide solvent known in the art can be used. Examples of silver halide solvents include:
(A) US Pat. Nos. 3,271,157 and 3,531,
289, 3,574,628, JP-A-54-10.
No. 19, No. 54-158917, and Japanese Patent Publication No. 58-3
Organic thioethers described in 0571, etc., (b)
Thiourea derivatives described in JP-A Nos. 53-82408, 55-29829, 57-77736 and the like,
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in JP-A-53-144319, (d) JP-A-54-10
No. 0717, etc., imidazoles, (e) sulfites, (f) thiocyanates, (g) ammonia,
(H) Ethylenediamines substituted with hydroxylalkyl as described in JP-A-57-196228,
(I) Substituted mercaptotetrazoles described in JP-A-57-202531, etc., (j) Water-soluble bromide,
(K) Benzimidazole derivatives described in JP-A-58-54333 and the like can be mentioned.

In the production of the silver halide photographic emulsion of the present invention, any of the acidic method, the neutral method and the ammonia method can be used.

In the production of the silver halide photographic emulsion of the present invention, halide ions and silver ions may be mixed at the same time, or one of them may be present while the other is mixed. Also, considering the critical growth rate of silver halide crystals,
Mixing halide and silver ions pAg and pH in the pot
It is also possible to control and add them sequentially or simultaneously. The halogen composition of the silver halide grains may be changed by using a conversion method at any step of silver halide formation.

In the production of the silver halide photographic emulsion of the present invention, a cadmium salt, a zinc salt, a lead salt, a thallium salt or an iridium salt is used in the step of nucleating silver halide grains and / or the step of growing the generated nuclei. Metal ions are added using at least one selected from (including complex salts), rhodium salts (including complex salts), salts of iron and other Group VIII metals (including complex salts), etc. These metals can be contained on the particle surface.

In the present invention, a twinned silver halide grain having two parallel twin planes facing each other can be used, but in that case, a tabular silver halide grain is preferable. The twin crystal is a silver halide crystal having one or more twin planes in one grain, and the morphology of the twin crystal is classified by Klein and Moiser in the article Photographic Correspondents ( Photographi
she Korrespondentz) Volume 99 99
Pp. 100, 57.

When tabular silver halide grains are used in the present invention, tabular silver halide grains account for 50% or more of the total projected area of the silver halide grains contained in the silver halide photographic emulsion of the present invention. It is preferably at least 60%, more preferably at least 80%.

When tabular silver halide grains are used in the present invention, the ratio of tabular silver halide grains having two twin planes parallel to the principal plane is 60% or more in terms of the number of silver halide grains. Preferably 70, more preferably 70
% Or more, more preferably 80% or more.

In the present invention, the tabular silver halide grain means a silver halide grain having an aspect ratio (ratio of diameter to thickness of silver halide grain) of 1.3 or more. The aspect ratio is preferably 3.0 or more, more preferably 5.0 or more.

In the production of the silver halide photographic emulsion of the present invention, a substance capable of forming a protective colloid can be used as a dispersion medium, but gelatin is preferably used.

In the present invention, when gelatin is used as the dispersion medium, the gelatin may be lime-treated, acid-treated, ion-exchanged, or the like. For more information on the gelatin manufacturing process, see Arthur Weiss, "The Macromolecular Chemistry of
Gelatin "(Academic Press, published 1964)
Etc.

Examples of substances that can form protective colloids other than gelatin include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate ester. Cellulose derivatives such as sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-n-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole and the like. There may be mentioned various synthetic or semi-synthetic hydrophilic polymeric substances such as mono- or copolymers.

The silver halide grains in the silver halide photographic emulsion of the present invention preferably have dislocation lines inside. The position where the dislocation line exists is not particularly limited, but it is preferable that the dislocation line exists near the outer peripheral portion of the silver halide grain, near the ridgeline, or near the apex. The dislocation line introduction position in the silver halide grain is preferably 50% or more, and more preferably 60% or more and less than 85% with respect to the total silver amount of the silver halide grain. The number of dislocation lines is preferably 30% or more (the number) of silver halide grains having 5 or more dislocation lines, but 5
It is more preferably 0% or more, still more preferably 80% or more. Further, in each case, the number of dislocation lines in one grain is preferably 10 or more, more preferably 20 or more, and further preferably 30 or more.

The method of introducing the dislocation lines into the silver halide grains is not particularly limited. For example, a method of adding an aqueous solution of iodine ion such as potassium iodide and a water-soluble silver salt solution by double jet, silver iodide. A method of adding fine particles, a method of adding only an iodine ion solution, JP-A-6-11781
A known method such as a method using an iodide ion-releasing compound described in JP-A No. 1994-154 is used.

In the production of the silver halide photographic emulsion of the present invention, reduction sensitization can be carried out by a method known in the art. The reduction sensitization may be performed during or after the formation of silver halide grains.

As a more specific method of reduction sensitization, a method called aging in the art, such as a method of aging and growing at low pAg by supplying silver ions to silver halide grains, an alkaline compound or the like is used. An arbitrary method or a combination thereof can be used because a method of increasing the pH to allow aging and growth, a method of adding a reducing agent, and the like are used.

When a reducing agent is used in the present invention, for example, thiourea dioxide, ascorbic acid and its derivatives, stannous salt, borane compounds, hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfurous acid. Salts and the like can be used, but thiourea dioxide, ascorbic acid and its derivatives, and stannous salt are preferably used.

In the production of the silver halide photographic emulsion of the present invention, an oxidizing agent known in the art can be used.
Examples of the oxidizing agent include hydrogen peroxide (water) and its adducts: H ₂ O ₂ , NaBO ₂ , H ₂ O ₂ -3H ₂ O, 2NaC.
_{O 3 -3H 2 O 2, Na} 4 P 2 O 7 -2H 2 O 2, 2Na 2 SO 4
Such as -H ₂ O ₂ -2H ₂ O. Peroxy acid salt: K ₂ S ₂ O ₃ ,
_{K 2 C 2 O 3, K} 4 P 2 O 3, K 2 [Ti (O) 2 C 2 O 4] -3
H ₂ O, peracetic acid, ozone, thiosulfonic acid compounds and the like can be mentioned.

In the production of the silver halide photographic emulsion of the present invention, the reduction sensitization and the addition of an oxidizing agent can be combined.

In the production of the silver halide photographic emulsion of the present invention, desalting can be performed for the purpose of suppressing the progress of physical ripening or removing unnecessary salts during or after the formation of silver halide grains. Desalting is carried out, for example, by Research Disclosure (Research Disc).
Hereinafter, abbreviated as RD. ) No. 17643, Item II.

More specifically, in order to remove unnecessary soluble salts from the precipitation product or the emulsion after physical ripening,
The Nudel water washing method in which gelatin is gelled may be used. Inorganic salts, anionic surfactants, anionic polymers (such as polystyrene sulfonic acid), or gelatin derivatives (such as acylated gelatin and carbamoylated gelatin) may be used. The precipitation method utilized can be used.

In addition, desalting utilizing membrane separation as described in Chemical Engineering Handbook, revised fifth edition (edited by the Chemical Engineering Society, Maruzen), pages 924 to 954, can be used.

Regarding the method of membrane separation, RD Vol. 102, Vol. 10208 and Vol. 131, Vol. 13122, or Japanese Patent Publication Nos. 59-43727, 62-270008 and JP-A-6-27008.
2-113137, 57-209823, 59
-43727, 62-131337, 61-2
19948, 62-23035, 63-401.
37, 63-40039, JP-A-3-14094.
No. 6, No. 2-172816, No. 2-172817,
The method described in JP-A-4-22942 can also be referred to.

In the production of the silver halide photographic emulsion of the present invention, the conditions other than the above are described in JP-A-61-66.
No. 43, No. 61-14630, No. 61-112142
No. 62-157024, No. 62-18556,
63-92942, 63-151618, 6
3-163451, 63-220238, 63
-311244, RD 365, 36544, 367
Appropriate conditions can be selected with reference to the volumes 36736, 391, 39121, and the like.

Additives used in constructing a color photographic light-sensitive material using the silver halide emulsion of the present invention are RD
17643, 18716 and 308119. Tables 1 and 2 show the relevant description locations.

[0092]

[Table 1]

[0093]

[Table 2]

When a silver halide emulsion of the present invention is used to form a color photographic light-sensitive material, various couplers can be used, specific examples of which are described in RD above. Table 3 shows the relevant sections.

[0095]

[Table 3]

Additives used in constructing a color light-sensitive material using the silver halide emulsion of the present invention are RD308.
It can be added by the dispersion method described in 119XIV. When a color light-sensitive material is constructed using the silver halide emulsion of the present invention, RD17643, page 28, RD18716, pages 647-648 and RD3.
Supports described in XVII of 08119 can be used.

The color photographic light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above-mentioned item RD308119VII-K.

The color photographic light-sensitive material using the silver halide emulsion of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above item RD308119VII-K. .

The silver halide emulsion of the present invention is a color negative film for general use or movies, a color reversal film for slides or televisions, color papers, color positive films, various color light-sensitive materials represented by color reversal papers, and monochrome. It can be applied to various black-and-white light-sensitive materials such as negative film, micro film, and X-ray film.

The color photographic light-sensitive material using the silver halide emulsion of the present invention is described in RD17643, 28-29.
Pages, RD18716, page 615 and RD308119,
It can be developed by the usual method described in XIX.

[0101]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these embodiments.

<< Preparation of Color Photosensitive Material >> A multi-layer color photosensitive material 101 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support having an undercoat layer. The addition amount of each material is shown in grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of the amount of silver, and the sensitizing dye (indicated by SD) is shown in the number of moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.30 CM-1 0.12 CC-1 0.03 OIL-1 0.24 Gelatin 1.33 Second Layer (Intermediate) Layer) Silver iodobromide emulsion j 0.10 AS-1 0.12 OIL-1 0.15 Gelatin 0.67 Third layer (low-sensitivity red color-sensitive layer) Silver iodobromide emulsion c 0.053 Odor Silver iodide emulsion d 0.11 Silver iodobromide emulsion e 0.11 SD-1 2.2 × 10 ⁻⁵ SD-2 5.9 × 10 ⁻⁵ SD-3 1.2 × 10 ⁻⁴ SD-4 1 .6 × 10 ^-4 SD-5 1.6 × 10 ^-4 C-1 0.19 CC-1 0.003 OIL-2 0.096 AS-2 0.001 Gelatin 0.44 Fourth layer (medium sensitivity Red-sensitive layer) Silver iodobromide emulsion b 0.28 Silver iodobromide emulsion c 0.34 Silver iodobromide emulsion d 0.50 SD-1 1.8 × 1 0 ^-5 SD-4 2.6 x 10 ^-4 SD-5 2.8 x 10 ^-4 C-1 0.74 CC-1 0.081 DI-1 0.020 DI-4 0.008 OIL-2 0.42 AS-2 0.003 Gelatin 1.95 Fifth layer (high-sensitivity red color sensitive layer) Silver iodobromide emulsion a 1.45 Silver iodobromide emulsion e 0.076 SD-1 2.3x 10 ⁻⁵ SD-2 1.1 × 10 ⁻⁴ SD-3 1.5 × 10 ⁻⁵ SD-4 2.1 × 10 ⁻⁴ C-2 0.087 C-3 0.12 CC-1 0. 036 DI-1 0.021 DI-3 0.005 BAR-1 0.024 OIL-2 0.15 AS-2 0.004 Gelatin 1.40 6th layer (intermediate layer) F-1 0.03 AS- 1 0.18 OIL-1 0.22 Gelatin 1.00 7th layer (low-sensitivity green color-sensitive layer) Silver iodobromide emulsion c 0.22 Silver iodobromide emulsion e 0 ^{22 SD-6 4.7 × 10 -5} SD-7 2.6 × 10 -4 SD-8 1.9 × 10 -4 SD-9 1.1 × 10 -4 SD-10 2.4 × 10 - ⁵ M-1 0.35 CM-1 0.044 DI-2 0.010 OIL-1 0.41 AS-2 0.001 AS-3 0.11 Gelatin 1.29 8th layer (medium sensitivity green color Functional layer) Silver iodobromide emulsion b 0.90 Silver iodobromide emulsion e 0.048 SD-6 3.8 × 10 ⁻⁵ SD-7 2.6 × 10 ⁻⁵ SD-8 3.4 × 10 ^{− 4} SD-9 ^{1.6x10 -4} SD-10 4.4x10 ^-5 M-1 0.15 CM-1 0.062 DI-2 0.032 OIL-1 0.28 AS-2 0. 005 AS-3 0.045 Gelatin 1.00 9th layer (high-sensitivity green color-sensitive layer) Silver iodobromide emulsion a 1.39 Silver iodobromide emulsion e 0.073 SD-6 4.1 × 10 ^{− Five} SD-7 2.6 × 10 ^-5 SD-8 3.7 × 10 ^-4 SD-10 4.9 × 10 ^-5 M-1 0.071 M-2 0.073 CM-1 0.013 DI- 2 0.004 DI-3 0.003 OIL-1 0.27 AS-2 0.008 AS-3 0.043 Gelatin 1.35 10th layer (yellow filter layer) F-2 0.050 F-30 0.060 AS-1 0.15 OIL-1 0.18 X-1 0.06 Gelatin 0.83 11th layer (low sensitivity blue color sensitive layer) Silver iodobromide emulsion g 0.22 Silver iodobromide emulsion h 0.099 Silver iodobromide emulsion i 0.17 SD-11 2.4 × 10 ⁻⁴ SD-12 5.7 × 10 ⁻⁴ SD-13 1.3 × 10 ⁻⁴ Y-1 1.02 OIL -1 0.42 AS-2 0.003 X-1 0.11 X-2 0.18 Gelatin 1.95 12th layer (high feeling Blue-sensitive layer) Silver iodobromide emulsion f 1.52 SD-11 8.3 × 10 -5 SD-12 2.3 × 10 -4 Y-1 0.22 DI-5 0.11 OIL-1 0.13 AS-2 0.003 X-1 0.15 X-2 0.20 Gelatin 1.20 13th layer (first protective layer) Silver iodobromide emulsion j 0.30 UV-1 0.11 UV -0.055 liquid paraffin 0.28 X-1 0.079 gelatin 1.00 14th layer (2nd protective layer) PM-1 0.13 PM-2 0.018 WAX-1 0.021 gelatin 0. 55 The characteristics of the silver iodobromide emulsion used above are shown below (the average grain size is the length of one side of a cube having the same volume).

Emulsion No. Average grain size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide emulsion a 0.85 4.2 7.0 Silver iodobromide emulsion b 0.70 4.2 6.0 Iodobromide Silver emulsion c 0.50 4.2 5.0 Silver iodobromide emulsion d 0.38 8.0 Octahedral twinned silver iodobromide emulsion e 0.27 2.0 14 tetrahedral regular silver iodobromide emulsion f 1.00 8.0 4.5 Silver iodobromide emulsion g 0.74 3.5 6.2 Silver iodobromide emulsion h 0.44 4.2 6.1 Silver iodobromide emulsion i 0.30 1. 9 5.5 Silver iodobromide emulsion j 0.03 2.0 1.0 The above sensitizing dyes were added to the above emulsions and ripened, and then triphenylphosphine selenide, sodium thiosulfate and chloroauric acid were added. , Potassium thiocyanate was added, and chemical sensitization was performed according to a conventional method so that the fog and the sensitivity were optimized.

In addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersion aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, weight average molecular weight: 10,000 and weight average molecular weight: 100,000.
2 kinds of polyvinylpyrrolidone (AF-1, AF-
2), inhibitors AF-3, AF-4, AF-5, hardener H
-1, H-2 and preservative Ase-1 were added.

The structures of the compounds used in the above samples are shown below.

[0107]

[Chemical formula 22]

[0108]

[Chemical formula 23]

[0109]

[Chemical formula 24]

[0110]

[Chemical 25]

[0111]

[Chemical formula 26]

[0112]

[Chemical 27]

[0113]

[Chemical 28]

[0114]

[Chemical 29]

[0115]

[Chemical 30]

[0116]

[Chemical 31]

[0117]

[Chemical 32]

The compounds shown in Table 4 were added to the 11th and 12th layers of Sample 101 at 8 mmo at the same time when the coupler was added.
Sample 102 was prepared in the same manner as 101 except that 1 / m ^{2 was} added.
~ 131 were produced.

[0119]

[Table 4]

[0120]

[Chemical 33]

<< Evaluation of Photographic Performance >><Evaluation of Sensitivity and Fog> After each sample was wedge-exposed with white light, the following development processing was performed to evaluate fog and sensitivity. The sensitivity was converted into a characteristic value by the reciprocal of the exposure amount that gives the minimum density +0.3 for the yellow density, magenta density, and cyan density of sensitometry.
It was expressed as a relative sensitivity with the sensitivity of 1 as 100, and the fog was shown by a value obtained by subtracting the density obtained when the processing except the color development step was performed in the processing step.

<Development treatment> Treatment process Treatment time Treatment temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach 45 seconds 38 ± 2.0 ° C. 150 ml fixation 1 minute 30 seconds 38 ± 2. 0 ° C. 830 ml stable 60 seconds 38 ± 5.0 ° C. 830 ml dry 1 minute 55 ± 5.0 ° C .- * Replenishment amount is a value per 1 m ² of the light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used. Color developer Water 800 ml Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl -N-Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 liter and potassium hydroxide or 20
Adjust to pH 10.06 with% sulfuric acid. Color development replenisher water 800 ml potassium carbonate 35 g sodium hydrogen carbonate 3 g potassium sulfite 5 g sodium bromide 0.4 g hydroxylamine sulfate 3.1 g 4-amino-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make 1 liter and potassium hydroxide or 20
Adjust the pH to 10.18 using%. Bleaching solution Water 700 ml 1,3-Diaminopropanetetrairon (III) acetate ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1 liter, and pH was adjusted to 4 with ammonia water or glacial acetic acid. Adjust to 4. Bleaching Replenisher Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting the pH to 4.4 using ammonia water or glacial acetic acid, add water. To 1 liter. Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter. Fixing replenisher Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter. Stabilizer and stable replenisher Water 900 ml Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g ammonia water 0.5 ml Water was added to make 1 liter, and then ammonia water or 5
Adjust to pH 8.5 with 0% sulfuric acid. The results are shown in Table 5.

[0124]

[Table 5]

<Evaluation of Pressure Resistance> Each sample was fixed under humidity control conditions of a relative humidity of 40%, one end with the emulsion surface inside, and bent along a stainless pipe having a diameter of 10 mm. These folds were made 10 seconds before exposure. After each sample subjected to this treatment was wedge-exposed with white light, the above-described development treatment was performed, and the obtained fog of yellow density (blue sensitive layer) was evaluated for the bent portion and the non-folded portion. The results are shown in Table 6.

[0126]

[Table 6]

As is clear from Tables 5 and 6, the compounds represented by the general formulas (1) to (6) according to the present invention have the same sensitivity and fog characteristics without deteriorating the photographic performance to other layers. Almost no effect of reduction is observed, and the excellent property of reducing fog is exhibited (while the comparative compound affects other layers). Further, the compounds represented by the general formulas (1) to (6) of the present invention have a reduced pressure fog density observed in the bent sample more than the effect of the compounds listed in the comparison.

[0128]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material excellent in pressure resistance, sensitivity and fog without adversely affecting other layers. Further, by being contained in the light-sensitive material, without adversely affecting other layers,
A specific hydroxylamine compound capable of providing a silver halide photographic light-sensitive material excellent in pressure resistance, sensitivity and fog can be provided.

Claims (11)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one compound represented by the following general formula (1). [Chemical 1] [In the formula, R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, W ₁ represents a silver affinity group or a dye residue, and L ₁₁ represents a linking group. l1
And l3 represent an integer of 1 or more, and l2 represents an integer of 0-4. ] 2. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (2) or general formula (3). [Chemical 2] [In the formula, W ₂ and W ₃ represent a silver affinity group or a dye residue, R ₂₁ and R ₃ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R ₂₂ is an alkyl group. Group, cycloalkyl group, aryl group, amino group,
Alkoxy group, aryloxy group, heterocyclic group, carboxamide group, sulfonamide group, hydroxylamino group, O-alkylhydroxylamino group, O-arylhydroxylamino group, hydrazino group, acyl group, alkyl or arylsulfonyl group, alkyl or An arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a silver affinity group, L ₁₂ and L ₁₃ each represent a linking group, and V ₂₁ , V ₂₂ and V ₂₃ represents a methine group or a nitrogen atom. However, V ₂₁ ,
At least one of V ₂₂ and V ₂₃ is a nitrogen atom.
m1 represents an integer of 0 to 4, and m2 represents an integer of 1 or more. ] 3. A compound represented by the following general formula (4)
Silver halide characterized by containing at least one
Photographic material. [Chemical 3] [In the formula, R₄₁Is a hydrogen atom, alkyl group, cycloalkyl
Represents a group, an aryl group or a heterocyclic group, and R₄₂Is Archi
Group, cycloalkyl group, aryl group, chlorine atom, bromine
Atom, fluorine atom, iodine atom, amino group, alkoxy
Group, aryloxy group, heterocyclic group, carboxamide
Group, sulfonamide group, hydroxylamino group, O-a
Rukylhydroxylamino group, O-arylhydroxy
Luamino group, hydrazino group, acyl group, alkyl or
Arylsulfonyl group, alkyl or aryl sulf
Inynyl group, carbamoyl group, sulfamoyl group, alco
Xycarbonyl group, aryloxycarbonyl group, ar
Represents a thio group or an arylthio group, V₄₁, V₄₂as well as
V₄₃Represents a methine group or a nitrogen atom. However, V₄₁, V
₄₂And V₄₃At least one of them is a nitrogen atom. X
Represents a heterocyclic group, Y represents a substituent, and n is 0 or more.
Represents an integer. ] 4. A silver halide photographic light-sensitive material characterized in that in the general formula (4), R ₄₂ is a substituted or unsubstituted hydroxylamino group. 5. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (5). [Chemical 4] [In the formula, R ₅₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, L ₁₅ and J represent a linking group, and V ₁ , V ₂ and V ₃ represent a methine group or a nitrogen atom. Represents However, at least one of V ₁ , V ₂ and V ₃ is a nitrogen atom. W ₅ represents a silver affinity group or pigment residue, m11 represents an integer of 0 to 4, m12 represents an integer of 1 or more. ] 6. A silver halide photographic light-sensitive material comprising at least one polymer containing a unit formed of a structure represented by the following general formula (6). Formula _{(6) HOR 6 N- (L} 16) in _q -P [wherein, R ₆ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, L ₁₆ represents a linking group, q represents 0 or 1, and P represents a polymerizable group containing an ethylenically unsaturated functional group. ] 7. A compound represented by the above general formula (1). 8. A compound represented by the above general formula (4). 9. A compound represented by the above general formula (5). 10. A compound represented by the above general formula (6). 11. A polymer compound formed from a structural unit represented by the above general formula (6).