JPH11344788A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material in which a high blackening density with high sensitivity and extremely high contrast is obtd. by using a stable developer, which realizes saving of the sensitizing dyes and low contamination of dyes, and which causes little changes in the sensitivity in the production process. SOLUTION: This silver halide photographic sensitive material has at least one spectrally sensitized photosensitive silver halide emulsion layer on a supporting body. The silver halide emulsion layer contains at least two kinds of silver halide emulsions having different addition concns. of nitrogen-contg. heterocyclic compds. which can form a complex with at least one kind of silver compd. The emulsion layer or other hydrophilic colloid layers contain as a nucleus forming agent, at least one kind of hydrazine deriv., and contain as a nucleus forming accelerator, at least one kind of amine deriv., onium salt, disulfide deriv. or hydroxymethyl deriv.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a super-high contrast silver halide photographic light-sensitive material used for photolithography.

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system exhibiting ultra-high contrast (especially γ of 10 or more) photographic properties in order to improve reproduction of continuous tone images or line images by halftone images. is necessary. There has been a demand for an image forming system that can be developed with a processing solution having good storage stability and obtain ultra-high contrast photographic characteristics. One of them is U.S. Pat. Nos. 4,166,742 and 4,16.
No. 8,977, No. 4,221,857, No. 4,2
No. 24,401, No. 4,243,739, No. 4,
Nos. 272,606 and 4,311,781, a surface latent image type silver halide photographic material to which a specific acylhydrazine compound is added, and a sulfurous acid preservative of 0.15 mol / l or more. PH included 11.0-12.
A system for forming a negative image having a super-high contrast of more than 10 by processing with a developing solution of No. 3 was proposed. This new image forming system can use only silver chlorobromide having a high silver chloride content in the conventional ultra-high contrast image forming system, but can also use silver iodobromide or silver iodochlorobromide. There are features. Another characteristic is that the conventional squirrel developer can contain only a trace amount of a sulfite preservative, but can contain a large amount of a sulfite preservative, so that it has relatively good storage stability.

[0003] European Patent Application Publication No. 0208514, JP-A-61-223732 and JP-A-63-46436 describe high contrast materials containing two kinds of silver halide grains and containing a hydrazine derivative. . These light-sensitive materials have been processed with a high pH (about pH 11.5) developer. However, a developer having a pH of 11 or more is easily oxidized by air and is unstable, and cannot withstand long-term storage or use.
In addition, high pH solutions are not environmentally desirable due to the care and handling of their waste liquids,
It is preferable to develop a silver halide photographic light-sensitive material containing a hydrazine compound with a developer having a lower pH to form a high contrast image.

However, if the pH of the developer is low, the effect of the hydrazine derivative on hardening is reduced, and a high-contrast image cannot be obtained. In order to promote high contrast, the development of more active hydrazine derivatives and nucleation accelerators has been attempted, but there have been cases where the long-term storage stability of the photosensitive material has been reduced.

The claims of Japanese Patent Application Laid-Open No. 4-331951 contain a hydrazine derivative and have been color sensitized at a higher concentration per surface area of silver halide grains as compared with other silver halide grains. High contrast photosensitive materials characterized by silver halide grains are described. Further, the claims of British Patent Application Publication No. 9407599 include silver halide grains spectrally sensitized with a non-desorbable sensitizing dye and silver halide grains not spectrally sensitized,
High contrast photosensitive materials containing hydrazine derivatives are described. In both cases, due to the presence of the hydrazine derivative, imagewise exposure and development contribute to the silver image in which spectrally sensitized photosensitive particles and non-spectrally sensitized non-photosensitive particles are generated, with high sensitivity, While maintaining the high concentration, there is an effect of saving the sensitizing dye and improving the residual color. However, in the former case, if the emulsion is kept in a mixed state for a long time, there is a disadvantage that the dye is made uniform and the sensitivity is lowered. The latter is limited to non-detachable dyes and is difficult to desorb from the emulsion, so that the residual color is not satisfactory. Further, these patents do not mention mixing of emulsions having different addition amounts of the nitrogen-containing heterocyclic compound in each emulsion.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a high sensitivity, a very high contrast and a high blackening density by using a stable developing solution, and at the same time, it is possible to save sensitizing dyes and to achieve low dye contamination. To provide a silver halide photographic material.
A further object of the present invention is to provide a silver halide photographic light-sensitive material having a small sensitivity fluctuation even in the production thereof.

[0007]

The object of the present invention is to provide (1)
On a support, there is provided at least one spectrally sensitized light-sensitive silver halide emulsion layer, and at least one nitrogen-containing heterocyclic compound capable of forming a complex with silver is contained in the silver halide emulsion layer. At least two kinds of silver halide emulsions contained at different concentrations, and at least one hydrazine derivative as a nucleating agent and an amine derivative as a nucleating accelerator in the emulsion layer or another hydrophilic colloid layer , A silver halide photographic material comprising at least one of an onium salt, a disulfide derivative or a hydroxymethyl derivative, and (2) the hydrazine derivative represented by the following general formula (N). Do (1)
Silver halide photographic light-sensitive material according to the item,

[0008]

Embedded image

(Wherein, R ₂₀ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₁₀ represents a hydrogen atom or a block group, and G ₁₀ represents —CO—, —COCO—, —C (= S)
_{-, - SO 2 -, -} SO -, - PO (R 30) - (R 30 has the same meaning as R _10, it may be the same as or different from R _10.)
Or an iminomethylene group. A ₁₀ and A ₂₀ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. (3) The nucleation accelerator is represented by the following general formula (A-1), general formula (A-2), or general formula (A-3)
Or a silver halide photographic material as described in the above item (1) or (2), which is at least one member selected from the formula (A-4):

[0010]

Embedded image

(Wherein R ₄ , R ₅ and R ₆ are alkyl groups,
Represents a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, or a heterocyclic group. Q represents a nitrogen atom or a phosphorus atom. L represents an m-valent organic group bonded to Q ⁺ at its carbon atom;
m represents an integer of 1 to 4. X ^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. A ₁ , A ₂ , A
₃ , A ₄ and Z each represent an organic residue containing a quaternized nitrogen atom for completing a substituted or unsubstituted unsaturated heterocyclic ring. B and C represent a divalent linking group. R ₁ , R
₂ represents an alkyl group, and R ₃ represents an alkyl group or an aralkyl group. However, R _{1 to} R ₆ , A _{1 to} A ₄ ,
Z, B, C or L has an anionic group in its substituent,
^When forming an internal salt with an unsaturated heterocycle containing a ⁺ or quaternized nitrogen atom, X ^n- is not required. ) And (4)
This has been attained by the silver halide photographic material as described in the above item (1), (2) or (3), wherein the average grain size is different in at least two kinds of silver halide emulsions.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The silver halide emulsion used in the present invention is obtained by mixing at least two types of emulsions having different addition amounts of a nitrogen-containing heterocyclic compound capable of forming a complex with at least one type of silver. Can be

In the present invention, the time at which the nitrogen-containing heterocyclic compound capable of forming a complex with at least one type of silver is added,
There is no particular limitation, and it may be any of during particle formation, before ripening, after ripening, and before coating, but it is desirable to mix them before coating.

The addition amount of the nitrogen-containing heterocyclic compound capable of forming a complex with at least one type of silver may be different as long as the total addition amount immediately before mixing the emulsion is different. The difference in the addition concentration of the nitrogen-containing heterocyclic compound capable of forming a complex with at least one type of silver is at least 1.1 times, preferably at least 1.5 times, the amount of silver contained in the emulsion. More preferably, the difference is more than twice.

In the present invention, a method of mixing emulsions having different addition amounts of a nitrogen-containing heterocyclic compound capable of forming a complex with at least one kind of silver can be used even if a small emulsion is added to an emulsion having a large addition amount. The reverse method may be used. Further, it is preferable that the emulsions having different addition amounts of the nitrogen-containing heterocyclic compound capable of forming a complex with at least one silver are spectrally sensitized with a desorbable spectral sensitizing dye and then mixed.

The nitrogen-containing heterocyclic compound of the nitrogen-containing heterocyclic compound capable of forming a complex with silver used in the present invention includes, for example,
Pyrazole ring, pyrimidine ring, 1,2,4-triazole ring, 1,2,3-triazole ring, 1,3,4-thiadiazole ring, 1,2,3-thiadiazole ring, 1,
2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,2,3,4-tetrazole ring, pyridazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1, 3,5-triazine ring, benzotriazole ring, benzimidazole ring, benzothiazole ring, quinoline ring, benzoxazole ring, benzoselenazole ring, naphthothiazole ring, naphthoimidazole ring, rhodanine ring, thiohydantoin ring, oxazole ring, thiazole Ring, oxadiazole ring, selenadiazole ring,
Examples include a naphthooxazole ring, an oxazolidinedione ring, a triazolotriazole ring, an azaindene ring (for example, a diazaindene ring, a triazaindene ring, a tetrazaindene ring, and a pentazaindene ring), a phthalazine ring, and an indazole ring.

Of these, compounds having an azaindene ring are preferable, and azaindene compounds having a hydroxy group as a substituent, for example, hydroxytriazaindene, tetrahydroxyazaindene, and hydroxypentazaindene compounds are more preferable. The heterocyclic ring may have a substituent other than the hydroxy group. Examples of the substituent include an alkyl group, an alkylthio group, an amino group, a hydroxyamino group, an alkylamino group, a dialkylamino group, an arylamino group, a carboxy group, an alkoxycarbonyl group, a halogen atom, an acylamino group, a cyano group, and a mercapto group. And the like.

The silver halide emulsion used in the present invention may contain a heavy metal which is a metal having a specific gravity of 5 or more, and more preferably contains a metal belonging to Group VIII. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, or the like. In order to increase sensitivity, K ₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ], K ₃ [Cr (C
N) The doping of a metal hexacyano complex such as ₆ ] is advantageously performed. In the present invention, as a preferred example of the silver halide emulsion having a difference in sensitivity between the silver halide emulsions, an emulsion having a difference in the type and / or amount of the contained Group VIII metal is mentioned. Specifically, the content of the rhodium compound and / or ruthenium compound and / or iridium compound in the low-sensitivity emulsion is set to 1.5 to 3 times the content of the rhodium compound and / or ruthenium compound and / or iridium compound in the high-sensitivity emulsion.
When the high-speed emulsion contains no rhodium compound and / or ruthenium compound and / or iridium compound, the low-speed emulsion contains the rhodium compound and / or ruthenium compound and / or iridium compound in an amount of 1 per mole of silver. × 10 ^-9 mol to 1 × 1
0 ^-5 mol is contained, it can be given a sensitivity difference by. At this time, it may be combined with a metal hexacyanoide complex dope which is preferably used for increasing the sensitivity. It is also preferable to combine with a difference in halogen composition and a type and / or degree of chemical sensitization.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, rhodium (III) halide compounds or rhodium complex salts having halogens, amines, oxalato, aquo, etc. as ligands, for example, hexachlororhodium (III) complex, pentachloroacolodium complex, tetrachlorodiacolate Rhodium complex salt, hexabromorhodium (II
I) Complex salts, hexaamine rhodium (III) complex salts, trioxalathrodium (III) complex salts and the like. These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of a rhodium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg KCl, NaCl, KBr,
NaBr) can be used. When preparing silver halide instead of using water-soluble rhodium,
It is also possible to add and dissolve another silver halide grain doped with rhodium in advance.

In the present invention, a ruthenium compound can be preferably used. Further, osmium and rhenium can be used. These compounds are disclosed in JP-A-63-2
No. 042, JP-A-1-2855941, JP-A-2-2085
No. 2, 2-20855, etc. in the form of a water-soluble complex salt. Particularly preferred is a six-coordinate complex represented by the following formula. [ML ₆ ] ⁿ -where M represents Ru, Re, or Os, L represents a ligand, and n represents 0, 1, 2, 3, or 4. In this case, any counter ion may be used, and examples thereof include an ammonium ion and an alkali metal ion. Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands, and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2- [Re (NO) (CN) ₅ ] ^2- [Re (O ) ₂ (CN) ₄ ) ^3- (RuCl ₆ ) ^3- (RuCl ₄ (H ₂ O) ₂ ) ^1- (RuCl ₅ (NO)) ^2- (RuBr ₅ (NS)) ^2- (Ru (CO) ₃ Cl _3] ^2- [Ru (CO) Cl _5] ^2- [Ru (CO) Br _5] ^2- [OsCl _6] ^3- [OsCl ₅ (NO)] ^2- [Os (NO) (CN) ₅ ] ^2- [Os (NS) Br ₅ ] ^2- [Os (CN) ₆ ] ^4- [Os (O) ₂ (CN) ₄ ] ^4-

The addition amount of these compounds is 1
1 × 10 per mole^-9Mol ~ 1 x 10 ^-FiveMolar range preferred
And particularly preferably 1 × 10^-8Mol ~ 1 x 10^-6Mole
It is. As the iridium compound used in the present invention
Is hexachloroiridium, hexabromoiridium
System, hexaammineiridium, pentachloronitrosi
Louisiridium and the like. Ironification used in the present invention
Compounds include potassium hexacyanoferrate (II),
Ferrous cyanate;

Hereinafter, specific examples of the nitrogen-containing heterocyclic compound according to the present invention will be listed, but it should not be construed that the invention is limited thereto. (N-1) 2,4-dihydroxy-6-methyl-1,
3a, 7-Triazaindene (N-2) 2,5-dimethyl-7-hydroxy-1,
4,7a-Triazaindene (N-3) 5-amino-7-hydroxy-2-methyl-1,4,7a-triazaindene (N-4) 4-hydroxy-6-methyl-1,3, 3
a, 7-Tetrazaindene (N-5) 4-hydroxy-1,3,3a, 7-tetrazaindene (N-6) 4-hydroxy-6-phenyl-1,3,
3a, 7-Tetrazaindene (N-7) 4-methyl-6-hydroxy-1,3,3
a, 7-Tetrazaindene (N-8) 2,6-dimethyl-4-hydroxy-1,
3,3a, 7-tetrazaindene (N-9) 4-hydroxy-5-ethyl-6-methyl-1,3,3a, 7-tetrazaindene (N-10) 2,6-dimethyl-4- Hydroxy-5
-Ethyl-1,3,3a, 7-tetrazaindene

(N-11) 4-hydroxy-5,6-
Dimethyl-1,3,3a, 7-tetrazaindene (N-12) 2,5,6-trimethyl-4-hydroxy-1,3,3a, 7-tetrazaindene (N-13) 2-methyl- 4-hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene (N-14) 4-hydroxy-6-methyl-1,2,2
3a, 7-Tetrazaindene (N-15) 4-hydroxy-6-ethyl-1,2,2
3a, 7-tetrazaindene (N-16) 4-hydroxy-6-phenyl-1,
2,3a, 7-tetrazaindene (N-17) 4-hydroxy-1,2,3a, 7-tetrazaindene (N-18) 4-methyl-6-hydroxy-1,2,2
3a, 7-tetrazaindene (N-19) 7-hydroxy-5-methyl-1,2,2
3,4,6-pentazaindene (N-20) 5-hydroxy-7-methyl-1,2,2
3,4,6-pentazaindene

(N-21) 5,7-dihydroxy-
1,2,3,4,6-pentazaindene (N-22) 7-hydroxy-5-methyl-2-phenyl-1,2,3,4,6-pentazaindene (N-23) 5- Dimethylamino-7-hydroxy-
2-phenyl-1,2,3,4,6-pentazaindene (N-24) 1-phenyl-5-mercapto-1,
2,3,4-tetrazole (N-25) 6-aminopurine (N-26) benzotriazole (N-27) 6-nitrobenzimidazole (N-28) 3-ethyl-2-methylbenzothiazolium p -Toluenesulfonate (N-29) 1-methylquinoline (N-30) benzothiazole

(N-31) Benzoxazole (N-32) Benzoselenazole (N-33) Benzimidazole (N-34) Naphthothiazole (N-35) Naphthoselenazole (N-36) Naphthoimidazole (N- 37) rhodanine (N-38) 2-thiohydantoin (N-39) 2-thio-2,4-oxazolidinedione (N-40) 3-benzyl-2-mercaptobenzimidazole

(N-41) 2-mercapto-1-methylbenzothiazole (N-42) 5- (m-nitrophenyl) tetrazole (N-43) 2,4-dimethylthiazole (N-44) 1-methyl -5-ethoxybenzothiazole (N-45) 2-methyl-β-naphthothiazole (N-46) 1-ethyl-5-mercaptotetrazole (N-47) 5-methylbenzotriazole (N-48) 5-phenyl Tetrazole (N-49) 1-methyl-2-mercapto-5-benzoylamino-1,3,5-triazole (N-50) 1-benzoyl-2-mercapto-5
Acetylamino-1,3,5-triazole

(N-51) 2-mercapto-3-aryl-4-methyl-6-hydroxypyrimidine (N-52) 2,4-dimethyloxazole (N-53) 1-methyl-5-phenoxybenzoxazole ( N-54) 2-Ethyl-β-naphthoxazole (N-55) 2-mercapto-5-aminothiadiazole (N-56) 2-mercapto-5-aminooxadiazole (N-57) 2-mercapto-5 -Aminoselenadiazole (N-58) 3- (5-mercaptotetrazole)-
Sodium benzenesulfonate (N-59) 3- (5-mercaptotetrazole)-
Sodium benzenecarboxylate

The addition amount of the nitrogen-containing heterocyclic compound varies over a wide range depending on the size, composition, and ripening conditions of silver halide grains.
mg to 1000 mg, particularly preferably 50 mg to 200 mg
mg from the monolayer on the silver halide grain surface.
It is preferable to add an amount capable of forming a zero molecular layer.
This addition amount can be adjusted by controlling the adsorption equilibrium state by a change in pH and / or temperature during aging. In the method of adding a nitrogen-containing heterocyclic compound to an emulsion according to the present invention, the nitrogen-containing heterocyclic compound can be added as a solution by dissolving it in a suitable solvent (for example, water or an aqueous alkali solution) that does not adversely affect the emulsion.

The proportion of silver halide emulsions having different addition amounts of the nitrogen-containing heterocyclic compound capable of forming a complex with at least one type of silver is not particularly limited. The ratio of the emulsion containing a small amount of the heterocyclic compound to the emulsion containing a large amount of the heterocyclic compound is 1: 1 to 1:20, more preferably 1: 1 to 1:10, based on the ratio of the amount of silver contained in the silver halide emulsion.
It is.

There is no particular limitation on the halogen composition of the silver halide emulsion used in the present invention, and silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide can be used. Any one may be used. The shape of silver halide grains is
Any of a cube, a tetrahedron, an octahedron, an irregular shape, and a plate shape may be used, but a cube or a plate shape is preferable. The photographic emulsion used in the present invention is Chimie et Physiqu by P. Glafkides.
e Photogrphique (Paul Montel, 1967),
GFDufin, Photographic Emulsion Chemistry (The
Focal Press, 1966), by VLZelikman et al
Making and Coating Photographic Emulsion (The Foca
l Press, 1964).

That is, any of an acidic method and a neutral method may be used, and the method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like. Is also good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 8, No. 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The amount of the silver halide solvent to be added varies depending on the type of the compound used, the intended grain size, and the halogen composition, but is preferably 2 × 10 ⁻⁵ to 10 ⁻² mol per mol of silver halide. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions. In order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-3
As described in JP-A-6890 and JP-A-52-16364, a method in which the addition rate of silver nitrate or alkali halide is changed in accordance with the grain growth rate, or a method disclosed in British Patent No. 4,24.
2,445, the method of changing the concentration of the aqueous solution as described in JP-A-55-158124,
It is preferred that the growth be performed quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion,
The coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is 0.5
μm or less, more preferably 0.1 μm to 0.1 μm.
4 μm. In the present invention, at least two types of silver halide emulsions containing different concentrations of the nitrogen-containing heterocyclic compound preferably have different grain sizes, and more preferably differ by 10% or more in average grain size side length.

The silver halide emulsion of the present invention is chemically sensitized.
Preferably. As a method of chemical sensitization, sulfur sensitization
Method, selenium sensitization, tellurium sensitization, noble metal sensitization, etc.
Known methods can be used, alone or in combination.
Used together. When used in combination,
For example, sulfur sensitization and gold sensitization, and sulfur sensitization and selenium sensitization
Sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization
Are preferred. The sulfur sensitization used in the present invention is generally
Usually, a sulfur sensitizer is added and the emulsion is heated at a high temperature of 40 ° C. or more.
This is performed by stirring for a certain period of time. As a sulfur sensitizer
Known compounds can be used.
In addition to sulfur compounds contained in tin, various sulfur compounds
Thiosulfates, thioureas, thiazoles,
Rhodanins and the like can be used. Preferred sulfurization
The compound is a thiosulfate or thiourea compound. Sulfur sensitization
The amount of the agent added depends on the pH, temperature, silver halide during chemical ripening.
It changes under various conditions such as particle size,
10 per mole of silver genide ^-7-10^-2Mole and better
Preferably 10^-Five-10^-3Is a mole.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-13489.
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 can be used. In particular, the general formula (VIII) in JP-A-4-322855
It is preferable to use the compound represented by (IX).
Further, a low-decomposition active selenium compound can also be preferably used. The low-decomposition-active selenium compound is a mixed solution of 10 mmol of AgNO ₃ , 0.5 mmol of a selenium compound, and 40 mmol of a 2- (N-morpholino) ethanesulfonic acid buffer in a water / 1,4-dioxane volume ratio of 1/1 ( pH =
6.3) is a selenium compound having a half-life of 6 hours or more when reacted at 40 ° C. This low-decomposition active selenium compound is disclosed in Japanese Patent Application No. 7-28881.
It is preferable to use the compounds of Compound No. 04, SE-1 to SE-10. The tellurium sensitizer used in the present invention is a compound that forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains.
The formation rate of silver telluride in the silver halide emulsion can be tested by the method described in JP-A-5-313284. Specifically, US Pat. No. 1,623,499
No. 3,320,069 and No. 3,772,01
No. 3, British Patent Nos. 235,211 and 1,121,
No. 496, No. 1,295,462, No. 1,39
No. 6,696, Canadian Patent No. 800,958, Japanese Patent Application Nos. 2-333819, 3-53693, and 3-13.
No. 1598, No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (198)
0), ibid 1102 (1979), ibid 645 (1
979), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin.
Trans.) 1; 2191 (1980), S. Pata
i) Hen, The Chemis of Organic Selenium and Tellurium Campounds
try of Organic Serenium and Tellunium Compounds), V
ol1 (1986) and Vol.2 (1987). In particular, Japanese Patent Application No. 4-14673.
Compounds represented by general formulas (II), (III) and (IV) in No. 9 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. Degrees can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention according to the method described in European Patent Application (EP) -293,917.

The light-sensitive silver halide emulsion of the present invention is spectrally sensitized to blue light, green light, red light or infrared light by a sensitizing dye. As sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes,
Styryl dye, hemicyanine dye, oxonol dye,
Hemioxonol dyes and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOS
URE Item 17643 IV-A (p.
23), Item 1831X (August 1979, p.4
37) or in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected. For example, A) for an argon laser light source, compounds (I) -1 to (I) -8 described in JP-A-60-162247;
No.-48653, compounds of I-1 to I-28,
I-1 to I-13 described in JP-A-4-330434
The compound described in U.S. Pat. No. 2,161,331
Compounds from ple 1 to Example 14, West German Patent 936,0
Compound Nos. 1 to 7 described in JP-A No. 71; B) Compounds of I-1 to I-38 described in JP-A-54-18726;
Compounds I-1 to I-35 described in JP-A No. 22 and compounds I-1 to I-34 described in JP-A-7-287338; C) For LED light sources, Japanese Patent Publication No. 55-3981
Dyes 1 to 20 described in JP-A No. 8 (Kokai) No. 62-28434.
Compounds I-1 to I-37 described in JP-A No. 3 and compounds I-1 to I-34 described in JP-A-7-287338.
Compounds of I-1 to I-12 described in JP-A-91032, compounds of I-1 to I-22 described in JP-A-60-80841, and compounds of I-1 to I- described in JP-A-4-335342. 29) and the compounds of I-1 to I-18 described in JP-A-59-192242, and E) the tungsten and xenon light sources of a plate making camera disclosed in JP-A-55-192242.
Compounds (1) to (19) represented by the general formula [I] described in JP-A-45015, and compounds described in Japanese Patent Application No. 7-346193.
-1 to I-97 and JP-A-6-24254
The compound of 4-A to 4-S described in No. 7, 5-A to 5
Compounds of -Q, compounds of 6-A to 6-T and the like are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Vol. 176, Volume 17643 (December 1978) No. 23
Section J on page IV or the aforementioned JP-B-49-25500
No. 43-4933, JP-A-59-19032,
No. 59-192242.

Two or more sensitizing dyes may be used in combination in the present invention. The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. As disclosed in JP-B-44-23389, JP-B-44-27555, and JP-B-57-22091, a dye is dissolved in an acid, and the solution is added to an emulsion. A method in which an acid or a base is added to an emulsion as an aqueous solution in the presence of an acid, US Pat. No. 3,822,135
No. 4,006,025, etc., a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
As disclosed in JP-A-102733 and JP-A-58-105141, a dye is directly dispersed in a hydrophilic colloid,
A method in which the dispersion is added to an emulsion;
As disclosed in Japanese Patent No. 624, a method of dissolving a dye using a compound that causes a red shift and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye to be used in the present invention may be added to the silver halide emulsion of the present invention at any stage of the emulsion preparation which has been found to be useful. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in JP-A Nos. 60-196,749 and the like, the stage before silver halide grain formation and / or desalting, during and / or after desalting and before the start of chemical ripening. As disclosed in JP-A-58-113920, any time immediately before or during chemical ripening, any time after chemical ripening and before coating, before the emulsion is coated, It may be added in the process. Further, as disclosed in U.S. Pat. No. 4,225,666 and JP-A-58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step. It may be added separately during the chemical ripening step or after the completion of the chemical ripening, or divided before and after the chemical ripening or during the step and after the completion.
You may change and add the kind of compound and the combination of a compound which are divided and added.

The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. An addition amount of 0.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

Gelatin is preferably used as a binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, but other hydrophilic colloids can also be used, and these can be used in combination with gelatin. Can also. For example, gelatin derivatives, graft polymers of gelatin and other high molecular compounds, proteins such as albumin, casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl Uses various kinds of synthetic hydrophilic polymer substances such as alcohols, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like, or a single or copolymer. be able to. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. In the present invention, the amount of gelatin applied as a binder is such that the amount of gelatin in the entire hydrophilic colloid layer on the side having the silver halide emulsion layer is 3 g / m ² or less (preferably 1.
0 to 3.0 g / m ² ), and the total gelatin content of the entire hydrophilic colloid layer on the side having the silver halide emulsion layer and the total hydrophilic colloid layer on the opposite side is 6.0 g / m ² or less. Yes,
Preferably it is 2.0-6.0 g / m < ² >.

The swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is 80.
To 150%, more preferably 90 to 1%.
It is in the range of 40%. The swelling ratio of the hydrophilic colloid layer is determined by measuring the thickness (d0) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic material. For 1 minute,
The swelled thickness (Δd) was measured, and the swelling ratio (%) = Δd ÷
It is determined by the formula of d0 × 100.

Examples of the support that can be used in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

The hydrazine derivative used in the present invention will be described. The hydrazine derivative used in the present invention is preferably a hydrazine derivative represented by the following general formula (N).

[0045]

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In the formula, R ₂₀ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ₁₀ represents a hydrogen atom or a block group, and G ₁₀ represents —CO—, —COCO—, —C (= S)
_{-, - SO 2 -, -} SO -, - PO (R 30) - group (R ₃₀
It is selected from the same range as the groups defined in R _10, may be different from R _10. ) Or iminomethylene group. A ₁₀ and A _{20 each} represent a hydrogen atom, or one of them represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (N), the aliphatic group represented by R ₂₀ is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 30 carbon atoms. . In the general formula (N), R
_The aromatic group represented by ₂₀ is a monocyclic or condensed-ring aryl group, such as a benzene ring and a naphthalene ring. The heterocyclic group represented by R ₂₀ is a monocyclic or condensed, saturated or unsaturated, aromatic or non-aromatic heterocyclic group, for example, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, Examples include a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, a piperidine ring, and a triazine ring. Preferred as R ₂₀ is an aryl group, and particularly preferred is a phenyl group.

R ₂₀ may be substituted. Representative examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group, an active methine group). Alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic group containing a quaternized nitrogen atom (eg, pyridinio group), acyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group ( (Including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, an amino group, (Alkyl, aryl, or heterocycle) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, A nitro group, a mercapto group, an (alkyl, aryl, or heterocycle) thio group, an (alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group,
An acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a group having a phosphoric amide or a phosphoric ester structure, and the like can be given.

These substituents may be further substituted with these substituents.

The substituent which R ₂₀ may have is preferably an alkyl group having 1 to 20 carbon atoms (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group,
Acylamino group, sulfonamide group, ureido group, sulfamoylamino group, imide group, thioureido group, phosphoric amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl Group, carbamoyl group, carboxy group (including its salt), (alkyl, aryl, or heterocycle) thio group, sulfo group (including its salt), sulfamoyl group, halogen atom, cyano group, nitro group and the like. .

In the general formula (N), R ₁₀ represents a hydrogen atom or a block group, and the block group is specifically an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Represents a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group.

The alkyl group represented by R ₁₀ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, a trifluoromethyl group, a difluoromethyl group,
-Carboxytetrafluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluorocarboxymethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, o-hydroxybenzyl group and the like. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, for example, a vinyl group, 2-ethoxycarbonylvinyl group, 2-trifluoro-2-methoxycarbonylvinyl group and the like. The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, such as an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed-ring aryl group is preferable, and an aryl group containing a benzene ring is particularly preferable. For example, a phenyl group, a 3,5-dichlorophenyl group,
Examples include a 2-methanesulfonamidophenyl group, a 2-carbamoylphenyl group, a 4-cyanophenyl group, and a 2-hydroxymethylphenyl group. The heterocyclic group is preferably a 5- or 6-membered, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group containing at least one nitrogen, oxygen and sulfur atom, such as a morpholino group, a piperidino group (N -Substituted), imidazolyl group, indazolyl group (such as 4-nitroindazolyl group), pyrazolyl group,
Examples include a triazolyl group, a benzimidazolyl group, a tetrazolyl group, a pyridyl group, a pyridinio group (such as an N-methyl-3-pyridinio group), a quinolinio group, and a quinolyl group.
Morpholino, piperidino, pyridyl, pyridinio, indazolyl and the like are particularly preferred.

As the alkoxy group, an alkoxy group having 1 to 8 carbon atoms is preferable, and examples thereof include a methoxy group, a 2-hydroxyethoxy group and a benzyloxy group. As the aryloxy group, a phenoxy group is preferable, and as the amino group, an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group (quaternized (Including a nitrogen-containing heterocyclic group containing a nitrogen atom). Examples of the amino group include 2,2,6,6-tetramethylpiperidine-
4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-
And a 3-pyridinioamino group. As the hydrazino group, a substituted or unsubstituted hydrazino group or a substituted or unsubstituted phenylhydrazino group (such as a 4-benzenesulfonamidophenylhydrazino group) is particularly preferred.

The group represented by R ₁₀ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₂₀ .

In the general formula (N), R_TenIs G_Ten-R_Tenof
The part is split from the residual molecule, -G _Ten-R_TenPart atom
Cyclization reaction that produces a cyclic structure containing
And examples thereof include, for example,
And those described in JP-A-3-29751.

The hydrazine derivative represented by the general formula (N) may have a built-in adsorptive group that adsorbs to silver halide. Examples of such an adsorbing group include alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercapto heterocyclic groups, and triazole groups, which are described in U.S. Pat. Nos. 195233, 59-200231, 59-201045, 59-201046, and 5
Nos. 9-201047, 59-201048, 59
-201049, JP-A-61-170733, and 6
1-270744, 62-948, 63-23
No. 4244, No. 63-234245, No. 63-234
No. 246. These adsorbing groups to silver halide may be precursors. As such a precursor, Japanese Unexamined Patent Publication No.
The groups described in No. 44 are exemplified.

R ₁₀ or R _{20 in} the general formula (N) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁₀ or R ₂₀ in the general formula (N) may contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the general formula (N) is a polymer having a hydrazino group. Represents, for example, JP-A-64-86134
No., JP-A-4-16938, JP-A-5-97091, WO95-
No. 32452, WO95-32453, Japanese Patent Application No. 7-3511
No. 32, Japanese Patent Application No. 7-351269, Japanese Patent Application No. 7-351168, Japanese Patent Application No. 7-351
Compounds described in JP-A-351287 and JP-A-9-179229 are exemplified.

R ₁₀ or R _{20 in} the general formula (N) represents a cationic group (specifically, a group containing a quaternary ammonium group, or a nitrogen-containing group containing a quaternized nitrogen atom). A group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, (alkyl, aryl,
Or a heterocycle) thio group, or a dissociable group (such as a carboxy group, a sulfo group, an acylsulfamoyl group, or a carbamoylsulfamoyl group) that can be dissociated by a base. Examples of those groups include, for example, JP-A-7-234471 and JP-A-5-333466.
JP-A-6-19032, JP-A-6-19031
JP-A-5-45761, U.S. Pat. No. 4,994,365.
No. 4,988,604, JP-A-7-25924
No. 0, JP-A-7-5610, JP-A-7-244348
And the compounds described in German Patent No. 4006032.

In the general formula (N), A ₁₀ and A _{20 each} represent a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a Hammett having a sum of substituent constants of -0.5. A phenylsulfonyl group substituted as described above), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more; Alternatively, a linear, branched, or cyclic substituted or unsubstituted aliphatic acyl group (here, examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxy group, a carboxy group, and a sulfo group. ))). A ₁₀ and A ₂₀ are most preferably a hydrogen atom.

Next, hydrazine derivatives which are particularly preferred in the present invention will be described. R ₂₀ is particularly preferably a substituted phenyl group, a ballast group via a sulfonamide group, an acylamino group, a ureido group, or a carbamoyl group, an adsorptive group to silver halide, a group containing a quaternary ammonium group,
Nitrogen-containing heterocyclic group containing a graded nitrogen atom, a group containing a repeating unit of an ethyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group, a group capable of dissociating in an alkaline developer (carboxy group) , A sulfo group, an acylsulfamoyl group, a carbamoylsulfamoyl group, etc.),
Alternatively, a hydrazino group capable of forming a multimer (-NHNH
—G ₁₀ —R ₁₀ ) is preferably substituted. R ₂₀ is most preferably a phenyl group substituted with a benzenesulfonamide group, and the substituent on the benzene ring of the benzenesulfonamide group has any one of the aforementioned groups directly or via a linking group. Is preferred.

Among the groups represented by R ₁₀ , when G ₁₀ is a —CO— group, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group is preferable. Preferred are a hydrogen atom, an alkyl group, and a substituted aryl group (an electron-withdrawing group or an o-hydroxymethyl group is particularly preferred as the substituent).
Most preferably, it is an alkyl group. G ₁₀ is -COCO-
In the case of a group, an alkoxy group, an aryloxy group, or an amino group is preferable, and a substituted amino group, specifically, an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group is particularly preferable. The G ₁₀ is -SO ₂ -
In the case of a group, R ₁₀ is preferably an alkyl group, an aryl group or a substituted amino group.

In the general formula (N), G ₁₀ is preferably-
It is a CO- group or a -COCO- group, particularly preferably a -CO- group.

Next, specific examples of the compound represented by formula (N) are shown below. However, the present invention is not limited to the following compounds.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

[Table 5]

[0070]

[Table 6]

[0071]

[Table 7]

[0072]

[Table 8]

[0073]

[Table 9]

[0074]

[Table 10]

[0075]

[Table 11]

As the hydrazine derivative used in the present invention, in addition to the above, the following hydrazine derivatives are preferably used. The hydrazine derivative used in the present invention can also be obtained by various methods described in the following patents.
Can be synthesized.

(Formula 1) described in JP-B-6-77138
And specifically the compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082, specifically, pages 8 to 1 of the publication
Compounds 1 to 38 on page 8. JP-A-6-23049
A compound represented by the general formula (4), the general formula (5) or the general formula (6) described in No. 7;
Compounds 4-1 to 4-10 described on page 26, compounds 5-1 to 5-42 described on pages 28 to 36, and 39
6-1 to 6-7. Compounds represented by the general formulas (1) and (2) described in JP-A-6-289520, specifically from page 5 to
Compounds 1-1) to 1-17) and 2-
1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same. Compounds represented by general formula (H) and general formula (Ha) described in JP-A-7-104426, specifically, compound H described on pages 8 to 15 of the same publication
-1 to H-44. A compound described in Japanese Patent Application No. 7-191007 characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group. , General formula (B), general formula (C), general formula (D), general formula (E), general formula (F), specifically, compounds N-1 to N-30. Japanese Patent Application No. 7-19
Compounds represented by the general formula (1) described in 1007, specifically, compounds D-1 to D-55 described in the same publication.

The hydrazine-based nucleating agent of the present invention can be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, It can be used by dissolving it in methylcellosolve or the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine nucleating agent of the present invention may be added to any layer of the silver halide emulsion layer or another hydrophilic colloid layer on the side of the silver halide emulsion layer with respect to the support. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleating agent of the present invention is 1 × 10 ⁻⁶ to 1 × per 1 mol of silver halide.
10 ⁻² mol is preferred, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol is more preferred, and 2 × 10 ^{−5 to} 5 × 10 ⁻³ mol is most preferred.

The nucleation accelerator used in the present invention includes
Examples include an amine derivative, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. Examples are listed below. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds A-1) to A-73) described in pages 49 to 58. JP-A-7-84
No. 331, (Chem. 21), (Chem. 22) and (Chem. 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and compounds of Nb-1 to Nb-12.

The nucleation accelerator used in the present invention includes compounds represented by the following general formulas (A-1), (A-2), (A-3) and (A-
The onium salt compound represented by 4) is most preferably used. This will be described in detail below. First, general formula (A-1) will be described.

[0082]

Embedded image

In the formula, R ₄ , R ₅ and R _{6 each} represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group or a heterocyclic group, which further has a substituent. It may be. L
Represents an m-valent organic group bonded to Q ⁺ and its carbon atom, wherein m represents an integer of 1 to 4. X ^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. Where R
_4, R _5, R ₆ or L has an anionic group in a substituent thereof, the case of forming the Q ⁺ and intramolecular salt, no X ^n- is required.

Examples of the groups represented by R ₄ , R ₅ and R ₆ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
Linear or branched alkyl groups such as -butyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, octadecyl group; aralkyl groups such as substituted or unsubstituted benzyl groups; cyclopropyl group, cyclopentyl group And cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, naphthyl group and phenanthryl group; alkenyl groups such as allyl group, vinyl group and 5-hexenyl group; cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group. An alkynyl group such as a phenylethynyl group; a heterocyclic group such as a pyridyl group, a quinolyl group, a furyl group, an imidazolyl group, a thiazolyl group, a thiadiazolyl group, a benzotriazolyl group, a benzothiazolyl group, a morpholyl group, a pyrimidyl group, or a pyrrolidyl group. No.

Examples of the substituent on these groups include, in addition to the groups represented by R ₄ , R ₅ and R ₆ , a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; Group, (alkyl or aryl) amino group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, carbonamide group, carbamoyl group, sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group (
Carboxylate), sulfonic acid group (including sulfonate), cyano group, oxycarbonyl group, acyl group and the like.

Examples of the group represented by L include groups having the same meaning as R ₄ , R ₅ and R ₆ when m represents 1.
In addition, when m represents an integer of 2 or more, a trimethylene group,
Polymethylene groups such as tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group, dodecamethylene group, etc., polyvalent groups such as arylene group such as phenylene group, biphenylene group and naphthylene group, trimethylenemethyl group, tetramethylenemethyl group etc. Alkylene group, phenylene-1,3,5-toluyl group, phenylene-1,2,4,
And a polyvalent arylene group such as a 5-tetrayl group.

Examples of the counter anion represented by X ^n- include halogen ions such as chloride ion, bromine ion and iodine ion, acetate ion, oxalate ion, and the like.
Examples include carboxylate ions such as fumarate ions and benzoate ions, sulfonate ions such as p-toluenesulfonate, methanesulfonate, butanesulfonate, and benzenesulfonate; sulfate ions; perchlorate ions; carbonate ions; and nitrate ions.

In the general formula (A-1), R ₄ , R ₅ ,
R ₆ is preferably a group having 20 or less carbon atoms, and when Q represents a phosphorus atom, an aryl group having 15 or less carbon atoms is particularly preferred. When Q represents a nitrogen atom, an alkyl group having 15 or less carbon atoms, aralkyl And aryl groups are particularly preferred. m is preferably 1 or 2, and when m represents 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group, an aralkyl group, or an aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group, an aralkylene group, or a combination of these groups with a —CO— group, a —O— group,
—N (NR ′) — group (NR ′ is a hydrogen atom or R ₄ , R
₅ , R ₆ represents a group having the same meaning as above, and when a plurality of NR's are present in the molecule, these may be the same or different, and may be bonded to each other), -S- Group,
₂ formed by combining a —SO— group and a —SO ₂ — group
Is a valence group. When m represents 2, L is preferably a divalent group having a total carbon number of 20 or less bonded to Q ⁺ at its carbon atom. When m represents an integer of 2 or more, R
_4, R _5, R ₆ each there are a plurality, the plurality of R _4, R _5, R ₆ may be different even in the same, respectively.

The counter anion represented by X ^n- is preferably a halogen ion, a carboxylate ion, a sulfonate ion or a sulfate ion, and n is preferably 1 or 2.

Many of the compounds represented by formula (A-1) of the present invention are known and are commercially available as reagents. As a general synthesis method, when Q is a phosphorus atom, a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester, or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method. is there. When Q is a nitrogen atom, there is a method of reacting a primary, secondary or tertiary amino compound with an alkylating agent such as an alkyl halide or a sulfonic acid ester.

Specific examples of the compound represented by formula (A-1) are shown below. However, the present invention is not limited to the following compounds.

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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Next, the general formula (A-2) and the general formula (A-
3) will be described.

[0100]

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In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent an organic residue for completing a substituted or unsubstituted unsaturated heterocycle containing a quaternary nitrogen atom, and a carbon atom ,
It may contain a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom, and the benzene ring may be condensed. A ₁ , A
Examples of the unsaturated hetero ring formed by ₂ , A ₃ and A ₄ include a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a thiazole ring, a thiadiazole ring, a benzotriazole ring, a benzothiazole ring, a pyrimidine ring and a pyrazole ring. And the like. Particularly preferred are a pyridine ring, a quinoline ring and an isoquinoline ring.

The divalent groups represented by B and C include alkylene, arylene, alkenylene, alkynylene, -SO
_2- , -SO-, -O-, -S-, -N (RN)-,-
What is constituted by C = O- and -P = O- alone or in combination is preferable. Here, RN represents an alkyl group, an aralkyl group, an aryl group, or a hydrogen atom. As particularly preferred examples, B and C are alkylene, arylene, -C = O
-, -O-, -S-, and -N (RN)-alone or in combination.

R ₁ and R ₂ are preferably an alkyl group having 1 to 20 carbon atoms, which may be the same or different. The alkyl group may be substituted by a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), An unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, etc.), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.),
(Alkyl or aryl) oxycarbonyl group, sulfo group (including sulfonate), carboxy group (including carboxylate), mercapto group, hydroxy group, alkoxy group (for example, methoxy group, ethoxy group, etc.),
Aryloxy group, carbonamido group, sulfonamido group, sulfamoyl group, carbamoyl group, ureido group,
A thioureido group, an (alkyl or aryl) amino group, a cyano group, a nitro group, an alkylthio group, an arylthio group and the like. Particularly preferably, R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms. Examples of preferred substituents include a carbamoyl group, an oxycarbonyl group, an acyl group, an aryl group, a sulfo group (including a sulfonate)
Carboxy group (including carboxylate) and hydroxy group.

The unsaturated heterocyclic ring formed by A ₁ , A ₂ , A ₃ and A ₄ together with the quaternized nitrogen atom may have a substituent. Examples of the substituent in this case are selected from the substituents described above as the substituent of the alkyl group of R ₁ and R ₂ . The substituent preferably has 0 to 10 carbon atoms.
Aryl group, alkyl group, carbamoyl group, (alkyl or aryl) amino group, oxycarbonyl group,
Alkoxy group, aryloxy group, (alkyl or aryl) thio group, hydroxy group, carbonamido group,
Sulfonamide group, sulfo group (including sulfonate),
And carboxy groups (including carboxylate).

With respect to the counter anion represented by X ^n- ,
The formula is the same as the formula (A-1), and the preferred range is also the same.

The compounds of the present invention can be easily synthesized by generally well-known methods.
v., 16, 163 (1962). Specific compounds of the general formulas (A-2) and (A-3) are shown below, but the invention is not limited thereto.

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[0108]

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[0109]

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[0110]

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Next, general formula (A-4) will be described.

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The nitrogen-containing unsaturated hetero ring containing Z may contain a carbon atom, a hydrogen atom, an oxygen atom, and a sulfur atom in addition to the nitrogen atom, and may further have a benzene ring fused thereto.
Further, it may have a substituent. Examples of the hetero ring formed include general formulas (A-2) and (A-3)
And the same as the examples of the nitrogen-containing unsaturated heterocyclic ring formed by A ₁ , A ₂ , A ₃ and A ₄ . The preferred range is also the same, and a pyridine ring, a quinoline ring and an isoquinoline ring are preferred. When the nitrogen-containing unsaturated heterocyclic ring containing Z has a substituent, examples of the substituent include those represented by A ₁ , A ₂ , A ₃ , and A _{4 in} formulas (A-2) and (A-3). Examples of the substituent which the nitrogen-containing unsaturated hetero ring to form may have may be the same as those mentioned above, and the preferred range is also the same.

R ₃ represents an alkyl group or an aralkyl group, which has 1 to 20 carbon atoms, may be substituted or unsubstituted, and may be linear or branched or cyclic. Examples of the substituent include R ₁ and R in the general formula (A-2).
Examples are the same as the examples of the substituent which the alkyl group represented by ₂ may have, and the preferred range is also the same. The counter anion represented by X ^n- is the same as that in formula (A-1), and the preferred range is also the same.

The compound represented by formula (A-4) of the present invention can be easily synthesized by a generally well-known method. For example, Quart. Rev., 16, 163 (196)
It can be synthesized by the method described in 2).

Next, specific examples of the compound represented by formula (A-4) of the present invention are shown below, but the present invention is not limited thereto.

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An amino compound is also preferably used as a nucleation promoting agent. Specifically, the following compounds are preferably used. Compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in JP-A-7-84331, specifically, compounds described on pages 6 to 8 of the same.
Compounds represented by the general formula [Na] described in JP-A-7-104426, specifically, compounds Na-1 to Na-22 described on pages 16 to 20 of the same. Patent application 7-378
No. 17 represented by general formulas (1), (2), (3), (4), (5), (6) and (7) Compounds, specifically, the compounds of 1-1 to 1-19 and 2-1 to 2- described in the same specification
22 compounds, 3-1 to 3-36 compounds, 4-1 to 4
-5, 5-1 to 5-41, 6-1 to 6
The compound of -58 and the compounds of 7-1 to 7-38.

The nucleation accelerator of the present invention may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl It can be used by dissolving it in Cellsolve or the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The nucleation promoting agent of the present invention is applied to a support.
The silver halide emulsion layer on the silver halide emulsion layer side or other
May be added to any of the hydrophilic colloid layers of
Silver colloid emulsion layer or hydrophilic colloid adjacent to it
It is preferably added to the metal layer. Nucleation accelerator of the present invention
The addition amount was 1 × 10 5 per mol of silver halide.^-6~ 2 × 10
^-2Mole is preferred and 1 × 10^-Five~ 2 × 10^-2Mole more
Preferably 2 × 10^-Five~ 1 × 10^-2Mole is most preferred
No. In the present invention, a nitrogen-containing heterocyclic compound, a nucleating agent, and a nucleating agent
The layers containing the accelerator may be the same or different.
Also, the content layer may be a plurality of layers unless otherwise specified.
No.

The processing agents such as the developing solution and the fixing solution and the processing method in the present invention are described below, but it goes without saying that the present invention is not limited to the following description and specific examples.

For the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used.

The developer used in the present invention (hereinafter, both the development starting solution and the development replenisher are collectively referred to as a developer).
The developing agent used for (1) is not particularly limited, but preferably contains a dihydroxybenzene or a hydroquinone monosulfonate, and may be used alone or in combination. Further, in terms of developing ability, dihydroxybenzenes and 1-phenyl-3
-Combinations of pyrazolidones or combinations of dihydroxybenzenes and p-aminophenols are preferred. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred.

As the developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention, 1-phenyl-3
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone and the like. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine as a p-aminophenol-based developing agent used in the present invention; o-methoxy-p- (N, N
-Dimethylamino) phenol, o-methoxy-p-
There are (N-methylamino) phenol and the like, and among them, N-methyl-p-aminophenol or Japanese Patent Application No. Hei.
Aminophenols described in 70908 and Japanese Patent Application No. 8-70935 are preferred.

The dihydroxybenzene-based developing agent is usually 0.1%.
It is preferably used in an amount of from 05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.23 mol / l to 0.5 mol / l. It is preferred to use the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

The developer for processing the light-sensitive material in the present invention can contain commonly used additives (for example, a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonate, boric acid described in JP-A-62-186259, JP-A-60-9
The sugars described in 3433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), and the like, preferably carbonates , Boric acid is used. The amount of buffer, especially carbonate, used is preferably at least 0.1 mol / l, in particular from 0.2 to
1.5 mol / l.

As the preservative used in the present invention, there are sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. Sulfite is used in an amount of 0.2 mol / l or more, especially 0.3 mol / l or more. However, if added in an excessively large amount, silver stain in a developing solution may be caused.
It is desirable to use liters. Particularly preferably, 0.35 to
0.7 mole / liter.

Examples of the additives used other than the above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (for example, sodium 3- (5-mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercapto Tetrazole, etc.) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness inhibitor. Further, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound may be contained as an antifoggant or a black pepper (black pepper) inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate,
5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-
Mercaptobenzotriazole and the like can be mentioned. The amount of these additives is usually from 0.01 to 10 mmol, more preferably from 0.1 to 2 mmol, per liter of the developer.

Further, various organic and organic compounds are contained in the developer of the present invention.
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelinic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

Examples of the aminopolycarboxylic acid include, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,
2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-
Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others JP-A-52-25632, 55-67747, 57-102624
And the compounds described in JP-B-53-40900. Organic phosphonic acids include, for example, U.S. Pat.
Hydroxyalkylidene-diphosphonic acid and Research Disclosure, Vol. 181, Item 18170 (1979) described in 3214454 and 3794591 and West German Patent Application No. 2227369.
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid.
Other examples include the compounds described in Research Disclosure 18170, JP-A-57-208554, JP-A-54-61125, JP-A-55-29883, and JP-A-56-97347.

Examples of the organic phosphonocarboxylic acid include those described in JP-A-52-102726, JP-A-53-42730, JP-A-54-121127 and JP-A-55-102127.
-4024, 55-4025, 55-126241, 55-65955, 55
-65956 and the aforementioned Research Disclosure 1817
0 and the like.

The organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10 ^-2 mol per liter of developer.

Further, as a silver stain inhibitor in the developer,
For example, JP-A-56-24347, JP-B-56-46585, JP-B-62
849, JP-A-4-362942 and JP-A-8-6215, as well as triazines having at least one mercapto group (for example, JP-B-6-23830, JP-A-3-282457, JP-A-7-175178).
And the pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4,6 -Trimercaptopyrimidine, etc.),
The same pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-
Trimercaptopyridine, compounds described in JP-A-7-248587, and the like pyrazines (eg, 2-mercaptopyrazine, 2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine Pyridazine (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3,4,6-
Trimercaptopyridazine, etc.), the compounds described in JP-A-7-175177, and the polyoxyalkyl phosphonates described in US Pat. These silver stain inhibitors can be used alone or in combination of two or more. The addition amount is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol, per liter of the developer. Also,
As the dissolution aid, compounds described in JP-A-61-267759 can be used. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hardening agent and the like may be contained.

The preferred pH of the developer is from 9.0 to 11.0, particularly preferably from 9.5 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As cations in the developer, potassium ions do not suppress the development as compared with sodium ions, and there is less jaggedness around the blackened portion called fringe. Furthermore, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, the molar ratio of potassium ion to sodium ion in the developer is preferably between 20:80 and 80:20. The ratio of the potassium ion to the sodium ion can be arbitrarily adjusted within the above range using a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishment amount of the developing solution was per 1 m ² of the photosensitive material.
330 ml or less, preferably 330 to 30 ml, most preferably 330 to 120 ml. The development replenisher may have the same composition and / or concentration as the development initiator, or may have a different composition and / or
Alternatively, it may have a concentration.

As the fixing agent of the fixing processing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent used can be changed as appropriate, but is generally about 0.7 to 0.7.
It is about 3.0 mol / liter.

The fixing solution of the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferred. Examples thereof include aluminum chloride, aluminum sulfate, carum alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are 0.01 to 0.1 as an aluminum ion concentration in the working solution.
It is preferably contained at 5 mol / l. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

If necessary, a preservative (for example, a sulfite, a bisulfite, a metabisulfite, etc.) may be used in the fixing treatment agent.
15 mol / l or more, preferably 0.02 mol / l to 0.3 mol / l), pH buffer (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, adipic acid, etc.) 0.1
Mol / l to 1 mol / l, preferably 0.2
Mol / l to 0.7 mol / l), compounds having an aluminum-stable light-sensitive material ability and water softening properties (eg, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid) , Maleic acid, glycolic acid, benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid,
Glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, saccharides,
0.001 mol / l to 0.5 mol /
Liter, preferably 0.05 mol / l to 0.3
Mol / l).

In addition, compounds described in JP-A-62-78551, pH adjusters (for example, sodium hydroxide,
Ammonia, sulfuric acid, etc.), a surfactant, a wetting agent, a fixing accelerator and the like. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and JP-A-57-6840.
And the known antifoaming agents can also be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, and thioureas described in JP-B-45-35754, JP-A-58-122535, and JP-A-58-122536. Derivatives, alcohols having triple bonds in the molecule, US Pat. No. 4,126,4
No. 59, thioether compounds described in JP-A-64-473;
9, mercapto compounds described in JP-A-1-4739, JP-A-1-159645 and JP-A-3-101728,
It can contain the mesoionic compound and thiocyanate described in JP-A-4-170539.

The fixing solution of the present invention has a pH of 4.0 or more, preferably 4.5 to 6.0. In the fixer, the pH rises due to the mixing of the developer with the processing, but in this case,
It is 6.0 or less, preferably 5.7 or less for a hardened fixer, and 7.0 or less, preferably 6.0 or less for a non-hardened fixer.
7 or less.

The replenishment rate of the fixing solution is 5 per m ² of the photosensitive material.
000 ml or less, preferably 300 ml or less, more preferably 200 to 60 ml. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, there is a Reclaim R-60 manufactured by Fuji Hunt. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

The photosensitive material which has been subjected to the development and fixing processing is then washed or stabilized (hereinafter, unless otherwise specified, washing including the stabilization processing is carried out. The liquid used for these is water or washing water. .) Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing liquid. The replenishment amount is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishment amount can be smaller. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping of an automatic developing machine can be eliminated. If washing with a low replenishment volume,
It is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A-63-18350 and JP-A-62-287252. Also, various oxidizing agents (eg, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

[0146] As a method of reducing the replenishing amount of the washing, a multi-stage countercurrent system (for example, two stages, three stages, etc.) than the old are the known water washing replenishment rate photosensitive material 1 m ² per 200 to 50
Milliliters are preferred. This effect can be similarly obtained by an independent multi-stage system (a method in which a new liquid is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, means for preventing water scale may be applied to the washing step. Any known means can be used as the means for preventing descaling, and the method is not particularly limited, but includes a method of adding a deodorant (so-called anti-descaling agent), a method of energizing, a method of irradiating ultraviolet rays or infrared rays or far-infrared rays, a magnetic field. , Ultrasonic treatment, heat, and emptying the tank when not in use. These scale prevention means may be performed according to the processing of the photosensitive material, may be performed at regular intervals irrespective of the state of use, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxide (for example,
-Mercaptopyridine-N-oxide, etc.) and may be used alone or in combination of two or more. Japanese Patent Application Laid-Open (JP-A) Nos. 3-224885 and 3-22468 disclose the method of energizing.
Nos. 7, 4-16280, 4-18980, etc. can be used.

In addition, a known water-soluble surfactant or defoamer may be added to prevent unevenness of water bubbles and transfer of dirt. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the washing system to prevent contamination by the dye eluted from the photosensitive material.

As described in JP-A-60-235133, a part or all of the overflow solution from the water washing step can be mixed and used with a processing solution having a fixing ability. In addition, microbial treatment (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Amount (BO
D) Compounds that reduce the chemical oxygen demand (COD), iodine consumption, etc. before draining, or filters that use a polymer having affinity for silver, or compounds that form poorly soluble silver complexes such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by, for example, adding silver to precipitate silver and filtering the mixture with a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment. Examples thereof include JP-A-2-201357, JP-A-2-132435, JP-A-1-102553, and JP-A-4-102553.
A bath containing the compound described in JP-A-6-44446 may be used as the final bath of the light-sensitive material. If necessary, a metal compound such as an ammonium compound, Bi, Al, etc., a fluorescent brightener, various chelating agents, pH adjustment of a film, a hardening agent, a bactericide, a deodorant, an alkanolamine or a surfactant may also be used in this stabilizing bath. Can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths and the stabilizing agents may be solid agents as in the above-mentioned developing and fixing agents.

It is preferable that the waste of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention is incinerated. These waste liquids are described in, for example, Japanese Patent Publication No. 7-83867,
It is also possible to condense or solidify with a concentrating device as described in U.S. Pat. No. 5,439,560 or the like before disposing.

To reduce the replenishing amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent the evaporation of the liquid and the oxidation of the air. U.S. Pat. Nos. 3,025,779 and 3,545,9 relate to roller transport type automatic developing machines.
No. 71, etc., and are simply referred to as a roller transport type automatic developing machine in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stopping step), but most preferably follows these four steps. Further, a rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, 25 to 25
To 160 seconds, the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each liquid is 25 to 50 ° C.
Is preferable, and 30 to 40 ° C. is preferable. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed with water may be squeezed with washing water, that is, dried through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. The drying method may be any method can be used, there is no particular limitation,
Hot air drying and JP-A-4-15534 and JP-A-5-2256
Roller drying and far infrared ray drying as disclosed in JP-A-5-289294, and a plurality of methods may be used in combination.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following places can be preferably used.

The polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5, specifically, compound (III) described in the same publication -1 to 25 compounds.

A compound represented by the general formula (I) described in JP-A-1-11832 and having substantially no absorption maximum in the visible region, specifically, a compound I- described in the same publication
Compounds 1 to I-26.

Antifoggants described in JP-A-2-103536, page 17, lower right, line 19 to page 18, upper right, fourth line.

Polymer latexes described in JP-A-2-103536, page 18, lower left line, line 12 to lower left line, line 20. General formula (I) described in Japanese Patent Application No. 8-13592.
A polymer latex having an active methylene group represented by the formula:
6. A polymer latex having a core / shell structure described in Japanese Patent Application No. 8-13592, specifically, compounds P-1 to P-55 described in the publication.

Matting agents, slip agents and plasticizers described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15;

Hardening agents described in JP-A-2-103536, page 18, upper right line, line 5 to line 17, upper right line.

Compounds having an acid group described in JP-A-2-103536, page 18, lower right, line 6 to page 19, upper left, first line.

JP-A-2-18542, page 2, lower left 1
The conductive substance described in the third line to the upper right line on page 3 of the publication. Specifically, the metal oxides described on page 2, right lower second line to page 10 lower right line, and conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

Water-soluble dyes described in JP-A-2-103536, page 17, lower right, line 1 to upper right, line 18;

Solid disperse dyes represented by formulas (FA), (FA1), (FA2) and (FA3) described in Japanese Patent Application No. 7-350753. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
(II-2) to (II-24) described in JP-A-7-152
No. 112, (III-5) to (III-18);
Nos. 152112 to (IV-2) to (IV-7).

Solid disperse dyes described in JP-A-2-294638 and JP-A-3-185773.

JP-A-2-12236, page 9, upper right 7
The surfactant described in the third line from the line on the lower right of the same page,
The PEC surfactant described in JP-A-103536, page 18, lower left line, line 4 to line 7, lower left line. JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5 fluorine-containing surfactants. Specifically, compounds IV-1 to VI-15 described in the publication.

Redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816. Preferably, the general formula (R-1) described in the publication,
Redox compounds represented by the general formulas (R-2) and (R-3). Specifically, compound R-1 described in the publication
~ R-68.

[0169]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of Emulsion A 1 liquid 1 liter water 20 g gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml Sodium chloride 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachlororhodium (III) (0.001% aqueous solution) 6 ml

Solution 1, solution 2 and solution 3 maintained at 40 ° C. and pH 4.5 were added simultaneously with stirring over 15 minutes.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10ml

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 100 mg of Exemplified Compound (N-4), phenoxyethanol as a preservative, and finally an average silver chloride of 70 mol%,
Containing 0.08 mol% of silver iodide, average grain size of 0.20 μm
A silver iodochloroiodobromide cubic emulsion A was obtained. (Coefficient of variation of particle size 10%)

Preparation of Emulsion B Emulsion B was prepared in the same manner as Emulsion A, and after chemical sensitization, 600 mg of Exemplified Compound (N-4) was added, and phenoxyethanol was added as a preservative to give an emulsion having an average particle size of 0.20 μm. B
I got

Preparation of Coated Sample 1 Emulsion A was subjected to spectral sensitization by adding 5.7 × 10 ⁻⁴ mol / mol Ag to sensitizing dye (1). Furthermore, KBr 3.4 × 10 ^-4
Mol / mol Ag, compound (1) 3.2 × 10 ⁻⁴ mol / mol Ag, compound (2) 8.0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, Citric acid 3.0 × 10 ⁻³ mol / mol Ag, compound (3) 1.5 ×
10 ^-4 mol / mol Ag, Compound (4) 6.0 × 10 ^-4 mol / mol Ag, the amount of further corresponding polyethyl acrylate latex and 0.01μm colloidal silica 30%, respectively gelatin binder ratio, aqueous 100 mg / m ^{2 of} latex (5), 150 mg / m ² of a dispersion of polyethyl acrylate, and a latex copolymer of methyl acrylate, sodium 2-acrylamido-2-methylpropanesulfonate and 2-acetoacetoxyethyl methacrylate ( Weight ratio 88: 5: 7) to 150 mg / m ² , core-shell type latex (core: styrene / butadiene copolymer (weight ratio 37/63), shell: styrene / 2-
Acetoacetoxyethyl methacrylate (weight ratio 84 /
16), the core / shell ratio = 50/50) was 150 mg /
m ² , 4 wt% of compound (6) based on gelatin was added, and the pH of the solution was adjusted to 5.5 using citric acid. They were coated on a subbed polyester support having a moisture-proof layer containing vinylidene chloride at a silver coating weight of 3.0 g / m ² and a gelatin coating weight of 1.3 g / m ² .

Upper layer of protective layer Gelatin 0.3 g / m ² 3.5 μm average silica matting agent 25 mg / m ² Compound (7) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (8) 50 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (9) 20 mg / m ² Compound (21) 25 mg / m ² Underlayer of protective layer Gelatin 0.5 g / m ² Compound (10) 15 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (6) 40 mg / m ² compound (11) 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Compound (12) 40 mg / m ² Compound (13) 20 mg / m ² Compound (14) 90 mg / m ² Compound (15) 40 mg / m ² Compound (16) 26 mg / m ² 1 2,3-divinylsulfonyl-2-propanol 60 mg / m ² Fine particles of polymethyl methacrylate (average particle size 6.5 μm) 30 mg / m ² Liquid paraffin 78 mg / m ² Compound (6) 120 mg / m ² Conductive layer Gelatin 0.1 g / m ² sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ²

[0177]

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[0178]

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[0179]

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Preparation of Coated Samples 2 to 6 Coated samples 2 to 6 were prepared in the same manner as coated sample 1 except that the amounts of emulsion and sensitizing dye (1) shown in Table 12 were changed when preparing coated sample 1. No. 6 was created.

Preparation of Coating Sample 7 When coating sample 1 was prepared, as shown in Table 13, sensitizing dye (1) was added to emulsion A at 5.7 × 10 ⁻⁴ mol / mol Ag (amount of coating sample 1). Coated sample 7 was prepared in the same manner as coated sample 1 except that an emulsion in which the added emulsion and the emulsion not containing sensitizing dye (1) added to emulsion A were mixed at a silver amount ratio of 1: 2. .

Preparation of Coated Sample 8 When preparing Coated Sample 1, as shown in Table 13, sensitizing dye (1) was added to Emulsion A at 5.7 × 10 ⁻⁴ mol / mol Ag (amount of Coated Sample 1). Coating sample 8 was prepared in the same manner as coating sample 1 except that the emulsion added and the emulsion not containing the sensitizing dye (1) added to emulsion B were used at a silver content of 1: 2. .

Preparation of Coating Sample 9 When preparing Coating Sample 1, as shown in Table 13, sensitizing dye (1) was added to Emulsion A at 2.9 × 10 ⁻⁴ mol / mol Ag (1/2 of coating sample 1). And the sensitizing dye in Emulsion A
(1) was changed to 2.9 × 10 ⁻⁴ mol / mol Ag (1 of coating sample 1).
Coating sample 9 was prepared in the same manner as coating sample 1 except that an emulsion in which the added emulsion was mixed with the added emulsion at a silver amount ratio of 1: 2 was used.

Preparation of Coating Sample 10 When preparing Coating Sample 1, as shown in Table 13, sensitizing dye (1) was added to Emulsion A at 2.9 × 10 ^-4 mol / mol Ag (1/2 of coating sample 1). And the sensitizing dye in Emulsion B
(1) was changed to 2.9 × 10 ⁻⁴ mol / mol Ag (1 of coating sample 1).
A coated sample 10 was prepared in the same manner as coated sample 1 except that an emulsion in which the added emulsion was mixed with the added emulsion at a silver amount ratio of 1: 2 was used.

Preparation of Coating Sample 11 When preparing coating sample 1, as shown in Table 13, sensitizing dye (1) was added to emulsion A at 1.9 × 10 ⁻⁴ mol / mol Ag (1/3 of coating sample 1). And the sensitizing dye in Emulsion B
(1) was changed to 1.9 × 10 ⁻⁴ mol / mol Ag (1 of coating sample 1).
Coating sample 11 was prepared in the same manner as coating sample 1 except that an emulsion in which the added emulsion was mixed with the added emulsion at a silver amount ratio of 1: 2 was used. When preparing the coating samples 1 to 11, samples having the same composition as the coating samples 1 to 11 were also prepared by changing the time from mixing to coating.

The obtained sample was exposed to xenon flash light having an emission time of 10 ⁻⁶ sec through a step wedge through an interference filter having a peak at 633 nm. Using the following developer A, AP-56 manufactured by Fuji Photo Film Co., Ltd.
0 After developing for 20 seconds at 35 ° C with an automatic developing machine,
Washing and drying were performed. The sensitivity was represented by the reciprocal of the exposure amount giving a density of 1.5, and the relative value of the sensitivity of each sample when the coating sample 1 was set to 100 was calculated as S1.5. The higher the value, the higher the sensitivity.

Developer A The composition of the developer A per 1 L of the concentrate is shown below. Potassium hydroxide 60.0 g Diethylenetriamine / pentaacetic acid 3.0 g Potassium carbonate 90.0 g Sodium metabisulfite 105.0 g Potassium bromide 10.5 g Hydroquinone 60.0 g 5-Methylbenzotriazole 0.53 g 4-Hydroxymethyl-4-methyl-1-phenyl-3 -Pyrazolidone 2.3 g Sodium 2-mercaptobenzimidazole-5-sulfonate 0.45 g 3- (5-Mercaptotetrazol-1-yl) sodium benzenesulfonate 0.15 g Sodium erythorbate 9.0 g Diethylene glycol 7.5 g Compound (17) 1.5 g Compound (18) 0.5 g pH 10.79 When using, dilute 2 parts of the above concentrate with 1 part of water. The pH of the working solution is 10.65.

[0188]

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The fixer used had the following formulation. (Formulation of fixing solution) Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g Add water to make 3 liters, and adjust to pH = 4.85 with sulfuric acid or sodium hydroxide. Replenishment volume is 250ml / m ²
I went in.

For the evaluation of the residual color, the sample was processed without exposure, and the sample was placed on a white paper and visually observed.
The processing conditions were the same as those for evaluating the photographic performance, except that the temperature of the washing water was kept at 10 ° C. or lower. The evaluation was performed on a 5-point scale of 5 (colorless), 4, 3 (with residual color), and 2, 1 (large residual color). The acceptable level is 4 or more. <Results> The samples of the present invention using the emulsions having different addition concentrations of the nitrogen-containing heterocyclic compound capable of forming the complex of the present invention are shown in Table 1.
As shown in FIG. 3, it was found that the sensitivity was high and the evaluation of the residual color was excellent, and the sensitivity was stable even when the emulsion mixing and dissolving time was long in the production.

[0191]

[Table 12]

[0192]

[Table 13]

Example 2 Preparation of Emulsion C Emulsion A was prepared in exactly the same manner as Emulsion A except that the time for adding Emulsion A and Emulsion A and Emulsion A and Emulsion A and Emulsion A and Emulsion A were adjusted. After the application, 800 mg of Exemplified Compound (N-4) was added, phenoxyethanol was added as a preservative, and finally, the average silver chloride content was 70 mol%, and silver iodide was 0.08%.
A silver iodochlorobromide cubic grain emulsion C having an average grain size of 0.18 .mu.m containing mol% was obtained. (Coefficient of variation of particle size 12%)

Preparation of Coated Sample 12 When preparing Coated Sample 1, as shown in Table 14, 5.9 × 10 ⁻⁴ mol / mol Ag (amount of Coated Sample 1) was added to Emulsion A with sensitizing dye (1). Coated sample 12 was prepared in exactly the same manner as coated sample 1 except that the emulsion obtained and the emulsion in which the sensitizing dye (1) was not added to Emulsion C were used at a silver ratio of 1: 3.

Preparation of Coated Sample 13 When preparing Coated Sample 1, as shown in Table 14, sensitizing dye (1) was added to Emulsion A at 2.9 × 10 ⁻⁴ mol / mol Ag (1/2 of Coated Sample 1). And the sensitizing dye added to Emulsion C
An emulsion prepared by mixing (1) with Emulsion B in an amount of 1.9 × 10 ^-4 mol / mol Ag (1/2 of the amount of the coated sample 1) in a silver amount ratio of 1: 3 was used. A coating sample 13 was prepared in exactly the same manner as the coating sample 1.

Preparation of Coating Sample 14 When preparing coating sample 1, as shown in Table 14, sensitizing dye (1) was added to emulsion A at 1.9 × 10 ^-4 mol / mol Ag (1/3 of coating sample 1). And the sensitizing dye added to Emulsion C
(1) was changed to 1.9 × 10 ⁻⁴ mol / mol Ag (1 of coating sample 1).
Coating sample 14 was prepared in the same manner as coating sample 1 except that an emulsion obtained by mixing the added emulsion with the added emulsion at a silver amount ratio of 1: 3 was used. Application samples 12 to 1 as in Example 1
When making 4, change the time until application after mixing,
Samples having the same composition as the coating samples 12 to 14 were also prepared.

The samples were evaluated for sensitivity and residual color in the same manner as in Example 1. At the same time, the blackening density when an exposure amount 2.5 times the exposure amount giving a density of 1.5 was measured as Dm. The results are shown in Table 14.

<Results> As shown in Table 14, the samples of the present invention using the emulsions having different addition concentrations of the nitrogen-containing heterocyclic compound capable of forming the complex of the present invention were the same even if the particle sizes were different. It can be seen that the sensitivity is high and the evaluation of the residual color is excellent, and the sensitivity is stable and the blackening density is very high even when the emulsion mixing and dissolving time is long in the production.

[0199]

[Table 14]

Example 3 In Example 2, sensitizing dye (2) was used in place of spectral sensitizing dye (1) at the time of preparing coating sample 14 to obtain 1.3 × 10 ^-4 mol / mol.
Mol Ag, sensitizing dye (3) at 1.3 × 10 ^-4 mol / mol A
A similar effect was obtained in a sample prepared in the same manner as in coating sample 14 of Example 2 except that g was added to emulsions A and C.

[0201]

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Example 4 In Example 2, a sensitizing dye (4) was used in place of the spectral sensitizing dye (1) at the time of preparing the coating sample 14, and the sensitizing dye (4) was 0.7 × 10 ⁻⁴ mol / mol.
Mol Ag, sensitizing dye (5) at 2.3 × 10 ^-4 mol / mol A
Samples were prepared in exactly the same manner as for coating sample 14 of Example 2 except that g was added to emulsions A and C. The sensitivity was evaluated in the same manner as in Example 2, except that the thus obtained coated sample was exposed through an interference filter having a peak at 488 nm instead of the interference filter having a peak at 633 nm. A similar effect was obtained.

[0203]

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Example 5 In Example 2, 2.7 × 10 ⁻⁵ mol / mol of the sensitizing dye (6) was used instead of the spectral sensitizing dye (1) when preparing the coated sample 14.
The procedure of Example 1 was repeated except that mol Ag was added, and compound (19) was added to emulsions A and C at 0.8 × 10 ^-4 mol / mol Ag and compound (20) was added at 0.5 × 10 ^-4 mol / mol Ag. A sample was prepared in the same manner as in the case of the application sample 14 of No. 2. The sensitivity was evaluated in the same manner as in Example 2 except that the coated sample thus obtained was exposed through an interference filter having a peak at 780 nm instead of the interference filter having a peak at 633 nm. A similar effect was obtained.

[0205]

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Example 6 In Examples 1 and 2, when preparing Emulsions A, B and C, 100 mg of Exemplified Compound (N-4) was all added, and Compounds (1) (Exemplified Compounds) were added to Emulsions A, B and C. (N-58))
D, E, and F to which 150 mg, 900 mg, and 1200 mg were added, respectively (the average particle size was 0.20 μm, respectively)
m, 0.20 μm, 0.18 μm). Using these emulsions, samples were prepared in the same manner as in Examples 1, 2 and 3, and the same evaluation was performed. As a result, the same effects were obtained. However, in Examples 1, 2, and 3, samples were prepared without adding the compound (1) added at the time of coating.

Example 7 Using the following developer B in place of the developer A, exposure and development were carried out in the same manner as in Example 2, and the coating samples 12 to 14 were evaluated. As a result, similar effects were obtained. .

Developer B Diethylenetriamine-5-acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium bicarbonate 25 g Sodium erythorbate 45 g N-methyl-p-aminophenol 7.5 g KBr 2 g 5-methylbenzotriazole 0.004 g 1-phenyl- 5-mercaptotetrazole 0.02 g sodium sulfite 10 g compound (17) 0.9 g compound (18) 0.3 g Water is added to 1 liter to adjust the pH to 9.7.

[0209]

The silver halide photographic light-sensitive material of the present invention comprises:
By containing at least two silver halide emulsions having different addition concentrations of the nitrogen-containing heterocyclic compound in the spectrally sensitized silver halide emulsion layer on the support, a conventional high pH developer can be obtained. Even without using it, it is possible to obtain a very hard and high blackening density. The light-sensitive material of the present invention has an excellent effect that the sensitivity is stable even when the emulsion mixing and dissolving time is lengthened in the production thereof with high sensitivity and little residual color.

Claims (4)

[Claims] 1. A support comprising at least one spectrally sensitized light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains at least one kind of compound capable of forming a complex with silver. At least two different concentrations of the nitrogen heterocyclic compound
And at least one hydrazine derivative as a nucleating agent and an amine derivative, onium salt, disulfide derivative or hydroxy as a nucleating agent in the emulsion layer or another hydrophilic colloid layer. A silver halide photographic material comprising at least one methyl derivative. 2. The silver halide photographic material according to claim 1, wherein the hydrazine derivative is represented by the following general formula (N). Embedded image (Wherein, R ₂₀ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ₁₀ represents a hydrogen atom or a block group, and G ₁₀ represents —CO—, —COCO—, —C (＝ S) —. , -SO ₂
-, - SO -, - PO (R 30) - (R 30 has the same meaning as R _10, R ₁₀ may be the same or different and.) Represents or iminomethylene group. A ₁₀ and A ₂₀ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. ) 3. The nucleation accelerator according to the following general formula (A-
The silver halide according to claim 1 or 2, wherein the silver halide is at least one selected from the group consisting of 1), general formula (A-2), general formula (A-3) and general formula (A-4). Photosensitive material. Embedded image (In the formula, R ₄ , R ₅ , and R ₆ represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, or a heterocyclic group.
Q represents a nitrogen atom or a phosphorus atom. L represents an m-valent organic group bonded to Q ⁺ and its carbon atom, and m represents an integer of 1 to 4. X ^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. A ₁ , A ₂ , A ₃ , A ₄ and Z each represent an organic residue for completing a substituted or unsubstituted unsaturated hetero ring containing a quaternized nitrogen atom.
B and C represent a divalent linking group. R ₁ and R ₂ represent an alkyl group, and R ₃ represents an alkyl group or an aralkyl group. However, when R _{1 to} R ₆ , A _{1 to} A ₄ , Z, B, C or L have an anionic group as a substituent thereof, the unsaturated heterocyclic ring containing a Q ⁺ or quaternized nitrogen atom and a molecule When forming an inner salt, X ^n- is not required. ) 4. The silver halide photographic material according to claim 1, wherein at least two kinds of silver halide emulsions have different average grain sizes.