JP2002296736A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a silver halide photographic sensitive material free of trouble of a sensor in an image setter, ensuring a small change of photographic performance even when the amount of a developing solution replenished is small and less liable to cause uneven development. SOLUTION: In the silver halide photographic sensitive material having at least one silver halide emulsion layer containing at least one photosensitive silver halide emulsion on the base, the silver halide emulsion layer or another hydrophilic colloidal layer contains a substantially non-photosensitive silver halide emulsion, the coating weight of the non-photosensitive silver halide is 10-200 mg/m<2> (expressed in terms of silver) and the transmittance of the sensitive material in the range of 900-950 nm has been lowered by >=4% on the average by incorporating the non-photosensitive silver halide emulsion. In the processing method, the silver halide photographic sensitive material is developed while replenishing <=250 ml/m<2> developing solution of pH 9.0-11.0 containing a compound of formula (I).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a method for processing an ultra-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 which can be developed with a processing solution having good storage stability and obtain ultra-high contrast photographic characteristics. One of them is US 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 sulfite preservative of 0.15 mol / l or more. PH included 11.0-12.
No. 3, a system for forming a negative image having a super-high contrast of more than 10 by processing with a developing solution has been 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 developing solution can contain only a trace amount of a sulfite preservative, but can contain a large amount of a sulfite preservative, so that the storage stability is relatively good.

[0003] With the recent demand for further low-replenishment and rapid processing, it has been desired to reduce the amount of coated silver. Has been vigorously done between. By making the particles fine, covering power (blackening density per unit silver amount) can be increased, and the amount of silver used can be reduced.

On the other hand, a system in which a photosensitive material supply cassette is automatically conveyed to an exposure machine and an automatic developing machine is becoming common. In this method, a film is detected by several optical sensors installed inside an exposure machine or the like. The optical sensor generally uses a light source in the infrared region that is outside the photosensitive wavelength of the photosensitive material, and is a method of detecting a film by scattering of silver halide particles or the like.

[0005] When silver halide grains are made finer, the infrared scattering intensity of the grains is reduced, so that there is a problem that detection failure of the above-mentioned sensor occurs, and improvement has been desired.

[0006] It is known to reduce the change in photographic performance by reducing the change in the pH value of the developer.
Stabilizing the photographic performance by increasing the buffer capacity of the developer is disclosed in Japanese Patent Publication No. 3-5730. However, when a fine grained silver halide photographic light-sensitive material is processed by an automatic processor using a developing solution having an increased buffering capacity, there is a disadvantage that uneven development is likely to occur.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to eliminate the problem of the sensor in the image setter, and to reduce the fluctuation of the photographic performance even if the replenishing amount of the developing solution is small. An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which causes less development unevenness.

[0008]

This problem has been solved by the following method. (1) In a silver halide photographic material having at least one silver halide emulsion layer containing at least one photosensitive silver halide emulsion on a support, the silver halide emulsion layer or another hydrophilic colloid The layer contains a substantially light-insensitive silver halide emulsion, the light-insensitive silver halide has a coating amount of 10 to ²⁰⁰ mg / m ^{2 in} terms of silver, and contains the light-insensitive silver halide emulsion. The silver halide photographic light-sensitive material whose transmittance from 900 nm to 950 nm has been reduced by 4% or more on average, containing a compound represented by the following general formula (I):
H9.0 to 11.0, the replenishing amount of the developer is 2
A method for processing a light-sensitive silver halide photographic material, wherein development is performed at 50 ml / m ² or less. (2) The non-light-sensitive silver halide emulsion has a silver bromide content of 80
(1) The method for processing a light-sensitive silver halide photographic material according to (1), comprising at least mol% of silver halide. (3) The method for processing a light-sensitive silver halide photographic material as described in (1) or (2), which comprises two or more different light-sensitive silver halide emulsions. (4) The method for processing a photosensitive silver halide photographic material according to (3), wherein the average grain size of the at least one photosensitive silver halide emulsion is 0.2 μm or less. (5) Processing of the light-sensitive silver halide photographic material according to any one of (1) to (4), wherein the silver halide emulsion layer or another hydrophilic colloid layer contains at least one hydrazine derivative. Method. General formula (I)

[0009]

Embedded image

In the formula, Y and Z are N or CR ₂ (R ₂ represents an alkyl group or an aryl group), and R ₁ is —SO ₃ M, —
_{COOM, -OH, -NHSO 2 R 3} , -SO 2 NR 3
Configuration through at least one substituted alkyl group, an aryl group or a heterocyclic group or an alkyl group, an aryl group or a heterocyclic group is a linking group selected from the group consisting of R ₄ and -NR ₅ CONR ₃ R ₄ Represents a group to be formed.
R ₃ , R ₄ and R ₅ represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. M is a hydrogen atom, an alkali metal atom,
Represents quaternary ammonium and quaternary phosphonium. In the present specification, “to” is a range including numerical values described before and after it as a minimum value and a maximum value.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The non-photosensitive silver halide grains used in the present invention have a halogen composition of silver bromide,
Any of silver chlorobromide, silver iodobromide, and silver iodochlorobromide can be used.
It is not more than 00 mol%. The shape of the silver halide grains may be any of cubic, tetrahedral, octahedral, irregular, and tabular, but is preferably cubic or tetradecahedral.

The non-photosensitive silver halide grains used in the present invention are described in Chimieet Physique Photogrp by P. Glafkides.
hique (Paul Montel, 1967), GF Dufi
n Photographic Emulsion Chemistry (The Focal Pr
ess, 1966), Making by VL Zelikman et al
and Coating Photographic Emulsion (The FocalPress
Ed., 1964) and the like. The substantially light-insensitive silver halide grains of the present invention have a blue region sensitivity of 1/10 or less of the photosensitive silver halide grains used in the photosensitive material of the present invention,
Preferably, it has not been spectrally sensitized. The non-photosensitive silver halide grains of the present invention can be subjected to surface modification such as metal complex dopant and chemical sensitization described in the section of photosensitive silver halide below. The non-light-sensitive silver halide grains of the present invention are preferably monodisperse grains, and Δ (standard deviation of grain size) /
(Average particle size) The coefficient of variation represented by｝ × 100 is 20% or less, more preferably 15% or less. The average grain size of the halogenated emulsion grains is preferably at least 0.1 μm, more preferably from 0.2 μm to 10 μm, even more preferably from 0.5 μm to 1.5 μm. The amount of the non-photosensitive silver halide grains used in the present invention varies depending on the grain size, but the addition of the non-photosensitive silver halide grains reduces the spectral transmittance of the light-sensitive material from 900 nm to 950 nm by 4% or more on average. Amount, preferably between 4% and 18%. 10 to 500 mg / m ² in terms of silver,
Preferably from 10 to 200 mg / ^{m 2.} 900nm
To 950 nm can be measured with a general spectrometer. For example, using a spectrometer U3500 manufactured by Hitachi, Ltd. with an integrating sphere installed at the light-receiving portion, a sample of a photosensitive material can be installed at the entrance of the integrating sphere for measurement.

The halogen composition of the silver halide emulsion used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver iodochlorobromide. However, in the present invention, two different halogen compositions are used.
One or more silver halide emulsions are on the same side of the support.

In the silver halide photographic light-sensitive material of the present invention, it is preferable to use two or more kinds of substantially different silver halide emulsions. Here, substantially different means, for example,
Physical properties refer to those with different grain shapes (normal crystal grains, tabular grains, etc.), grain size, halogen composition, etc.
Photographically, it means that sensitivity, gradation, covering power, and the like are different. Specifically, it refers to two or more types of silver halide emulsions prepared by different preparation methods, and in the distribution of one type of silver halide emulsion prepared by the same preparation method, It does not indicate a difference. For example, a silver halide emulsion having different sensitivities means that there is a difference in sensitivity between different types of silver halide emulsions at the same exposure wavelength. When the same sensitizing dye is used, the distribution sensitivity of the silver halide emulsion is determined by the difference in the average grain size of silver halide grains, the difference in halogen composition, the type and amount of heavy metal contained in the grains, and the chemical sensitization. It can be changed depending on the degree, the grain shape, or the amount adsorbed on the silver halide grains. Further, the same particle size, halogen composition, and particle shape are changed by using different sensitizing dyes. Therefore, there can be a difference in sensitivity due to a difference in grain size, a difference in halogen composition, a difference in heavy metals contained in the grains, a difference in the degree of chemical sensitization, a grain shape, and use of a different sensitizing dye.

The halogen compositions of the two or more silver halide emulsions preferably differ in silver bromide content by 10 mol% or more, and at least one of them has a silver bromide content of 50 mol% or more. It is preferable that the other one has a silver bromide content of 50 mol% or less.

The ratio of the combination of different types of silver halide emulsions is not particularly limited, but the ratio of high-sensitivity emulsions is preferably small, and the ratio of silver contained in the silver halide emulsion is 1: 1. １ ： 1: 20, more preferably 1: 2
１ ： 1: 10.

The different types of silver halide emulsions may be contained in the same layer or different layers. When different types of silver halide emulsions are mixed and coated on the same layer, the emulsion may be mixed by adding different types of silver halide emulsions and then adding a sensitizing dye to the same layer. The sensitizing dyes may be added to the silver halide emulsion and then mixed. When the silver halide emulsion is mixed after the addition of the sensitizing dye, the sensitizing dye used may be the same or different.

The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but is preferably cubic or tabular.

The photographic emulsion used in the present invention is P. Glafk
by ides Chimie et PhysiquePhotographique (Pa
ul Montel, 1967), by GF Dufin
Photographic Emulsion Chemistry (The Focal Press
Publishing, 1966), Making an by VLZelikman et al
d Coating Photographic Emulsion (The FocalPress
Ed., 1964) and the like.

That is, any of an acidic method and a neutral method may be used, and the method of reacting a soluble silver salt with a soluble halide 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. Particle size to the type and purpose of the addition amount of the compound used in the silver halide solvent varies depending halogen composition, ^10-5 to ^-2 mol per mol of silver halide is preferred. Further, the particles may be formed in the presence of a nitrogen-containing heterocyclic compound which forms a complex with silver. preferable. The addition amount of these compounds, pH, temperature, varies over a range of equivalent under various conditions such as the size of the silver halide grains, per mol of silver halide, ^{10-6 over 2} moles Is preferred. The addition of these compounds can be appropriately performed at each stage before, during, or after the formation of the particles, and is particularly preferably performed at the time of the formation of the particles.

According to the controlled double jet method and the grain formation method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and is used in the present invention. It is a useful tool for making silver halide emulsions. In order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method of changing the addition rate of silver nitrate or an alkali halide in accordance with the grain growth rate, a method disclosed in British Patent No. 4,242,445, 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in the above paragraph to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodispersed emulsion, and {(standard deviation of particle size) / (average particle size)} × 1.
The coefficient of variation represented by 00 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm or less.
It is 1 μm to 0.4 μm.

The photosensitive silver halide emulsion used in the present invention may be used alone or in combination of two or more. When two or more types are used, the particle sizes are preferably different. It is desirable that the difference between the particle sizes differs by 10% or more as the average particle side length.

The ratio of the combination of two or more silver halide emulsions used in the present invention is not particularly limited, but the emulsion containing a small amount of a nitrogen-containing heterocyclic compound capable of forming a complex with silver and the emulsion containing a large amount thereof are used. Is the ratio of the amount of silver contained in the silver halide emulsion to 1: 1 to 1:20, more preferably 1: 1 to 1:20.
1:10.

The silver halide emulsion used in the present invention is preferably a mixture of 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.

The addition amount of the nitrogen-containing heterocyclic compound capable of forming a complex with 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 silver is at least 1.1 times, preferably at least 1.5 times, more preferably at least 1.5 times as much as the amount of silver contained in the emulsion. Preferably, they differ by a factor of two or more.

The timing of adding the nitrogen-containing heterocyclic compound capable of forming a complex with silver is not particularly limited, and the silver halide emulsion may be formed during grain formation, before ripening, after ripening, or before coating. Either is fine.

The method of mixing the above-described emulsions having different addition amounts of the nitrogen-containing heterocyclic compound capable of forming a complex with silver may be a method of adding a small amount of emulsion to a high addition amount of emulsion, or vice versa.

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 a 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.

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) Rhodanin (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 surface of the silver halide grains.
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. According to 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 alkaline solution) that does not adversely affect the emulsion.

The silver halide emulsion used in the present invention is:
It may contain a metal belonging to Group VIII. In order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, a rhenium compound, a chromium compound and the like. Preferred as these heavy metals are metal coordination complexes, and hexacoordinate complexes represented by the following general formula. [M (NY) _m L _6-m ] ^n- (where M is a heavy metal selected from Ir, Ru, Rh, Re, Cr and Fe. L is a bridging ligand. Y is oxygen or M = 0, 1, 2 and n = 0,
1, 2, and 3. Preferred specific examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellurocyanates Nate, acid and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. In order to increase the sensitivity, an iron compound is preferably contained, and a metal coordination complex having a cyan ligand as a ligand is particularly preferable. These compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of the compounds, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid,
Hydrofluoric acid, etc.) or alkali halides (for example, K
Cl, NaCl, KBr, NaBr, etc.) can be used. It is also possible to add and dissolve another silver halide grain doped with these compounds in advance. Specific examples of the metal coordination complex are shown below. 1. [Rh (H ₂ O) Cl ₅ ] ^2-2 . [RuCl _6] ^3- 3. [Ru (NO) Cl ₅ ] ^2-4 . [RhCl _6] ^3- 5. [Ru (H ₂ 0) Cl ₅ ] ^{2 -6} . _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 7. [Ru ₂ Cl ₁₀ O] ^6-8 . [Re (NO) Cl ₅ ] ^2-9 . [Ir (NO) Cl _5] ^2- 10. [Ir (H ₂ 0) Cl _5] ^2- 11. [Re (H ₂ 0) Cl _5] ^2- 12. [RhBr _6] ^3- 13. [ReCl _6] ^3- 14. [IrCl _6] ^3- 15. _{[Re (NS) Cl 4 (SeCN} ) ] ^{2 -} 16. [Cr (CN) _6] ^3- 17. [Fe (CN) _6] ^3-

The addition amount of these compounds is from 1 × 10 ^{-8 to} 5 × 10 ^-6 mol, preferably from 5 × 10 ^-8 to 1 × 10 ^-6 mol, per mol of silver of the silver halide emulsion. Further, the above heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grains is not particularly limited, and may be a uniform distribution, a core-shell type having a different distribution between the surface and the inside, or a continuous distribution. The addition of these compounds can be appropriately performed during the production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them during emulsion formation and incorporate them into the silver halide grains. .

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination,
For example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, and sulfur sensitization, tellurium sensitization and gold sensitization are preferable.

The sulfur sensitization used in the present invention is generally carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain time. Known compounds can be used as the sulfur sensitizer, for example,
In addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used. Other U.S. Pat. Nos. 1,574,944 and 2,410,689
No. 2,278,947 and No. 2,728,66
No. 8, No. 3,501, 313, No. 3,656, 9
No. 55, German Patent 1,422,869, JP-B-56-24937, JP-A-55-45016 and the like can also be used. Preferred sulfur compounds are thiosulfates and thiourea compounds. The amount of the sulfur sensitizer to be added depends on the pH during chemical ripening,
Temperature, varies under various conditions such as the size of the silver halide grains, per mol of silver halide 10 ^-7 to 10 ^-2
Mol, more preferably 10 ^-5 to 10 ^-3 mol.

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, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-1.
No. 3489, JP-A-4-25832, JP-A-4-1092
It is preferable to use the compounds described in JP-A Nos. 40 and 4-324855. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, Selenopropions, 2-
Selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like. Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. For those skilled in the art, speaking of unstable selenium compounds as sensitizers for photographic emulsions,
As long as selenium is unstable, the structure of the compound is not critical, and the organic portion of the selenium sensitizer molecule carries selenium and has nothing to do with it being present in the emulsion in an unstable form. Is generally understood to have no role. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. The non-labile selenium compound used in the present invention is disclosed in JP-B-46-4553.
No., JP-B-52-34492 and JP-B-52-34
No. 491 can be used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof. In particular, JP-A-4-324855
It is preferable to use the compounds represented by the general formulas (VIII) and (IX) in the above. Further, a low-decomposition active selenium compound can also be preferably used. The low-decomposition-active selenium compounds are AgNO ₃ 10 mmol, selenium compound 0.5
The selenium when a mixed solution (pH = 6.3) of 40 mmol of a 2-mmol, 2- (N-morpholino) ethanesulfonic acid buffer in water / 1,4-dioxane at a volume ratio of 1/1 was reacted at 40 ° C. A selenium compound having a compound half life of 6 hours or more. The selenium compound can be analyzed by HPLC or the like to determine the half-life. The low-decomposition active selenium compound is disclosed in JP-A-9-1668.
It is preferable to use the compounds of 41 compound examples SE-1 to SE-8.

The tellurium sensitizer used in the present invention is a compound which 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 a silver halide emulsion is described in
It can be tested by the method described in No. 31284.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
3, No. 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ib
id 1102 (1979), ibid 645 (197)
9), Journal of Chemical Society
Perkin Transaction (J.Chem.Soc.Perkin.Tra)
ns.) 1, 191 (1980), S. Patai
Ed., The Chemistr of Organic Selenium and Tellurium Companies
y of Organic Serenium and Tellunium Compounds), Vo
11 (1986) and Vol. 2 (1987). In particular, JP-A-5-3132
Compounds represented by formulas (II), (III) and (IV) in No. 84 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention, the silver halide grains to be used, but the chemical ripening condition and the like and, generally, per mol of silver halide 10 ^-8 to 10 ^-2 mol, 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. As the gold sensitizer, the oxidation number of gold may be +1 or +3, and gold compounds generally used as gold sensitizers can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide and the like. About 10 ^-7 to 10 ^-2 mol can be used per 1 mol of silver halide.
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. The silver halide emulsion of the present invention can be prepared by using a European Patent (E)
P) -293,917, a thiosulfonic acid compound may be added. The silver halide emulsion in the light-sensitive material used in the present invention, two or more in the same layer,
Metal complexes with different types, distributions, contents, crystal habits, shapes, chemical sensitizers, added amounts, different sensitizing conditions, spectral sensitizing dyes, added amounts, spectral sensitization Those having different sense conditions may be used in combination, and furthermore, these layers may have a multilayer structure.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye depending on the use of the light-sensitive material. Good. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE
Item 17643 IV-A (p.2 December 1978
3), Item 18341X (p. 43, August 1979)
It is described in the literature described or cited in 7).
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 of (I) -1 to (I) -8 described in JP-A-60-162247;
No. 8653, compounds I-1 to I-28, JP-A-4-330434, compounds I-1 to I-13, and Exam described in U.S. Pat. No. 2,161,331.
Compounds from ple1 to Example14, West German Patent 9
36,071; B) For helium-neon laser and red laser diode light source, compounds of I-1 to I-38 described in JP-A-54-18726; Compounds of I-1 to I-35 described in JP-A-6-75322 and JP-A-7-2873
No. 38, compounds I-1 to I-34, and JP-A-2822138, 2-1 to 2-14, 3-
(1) to 3- (14), compounds of 4-1 to 4-6,
C) For LED light sources, compounds of Dyes 1 to 20 described in JP-B-55-39818, compounds of I-1 to I-37 described in JP-A-62-284343, and JP-A-7-2
Nos. 87338 to I-34, 2-1 to 2-1 described in Patent Publication No. 2822138.
4, 3- (1) to 3- (14), compounds of 4-1 to 4-6; D)
Compounds of I-1 to I-12 described in JP-A-1901032 and compounds of I-1 to I- described in JP-A-60-80841.
Compound No. 22 described in I-I-6 described in JP-A-4-335342.
Compounds from 1 to I-29 and JP-A-59-19224
Compounds I-1 to I-18 described in No. 2, E) Tungsten and xenon light sources for plate making cameras are represented by the general formula [I] described in JP-A-55-45015 (1). To (19), JP-A-6-24247
4-A to 4-S, 5-A to 5-
Q compound, 6-A to 6-T compound and
The compounds of I-1 to I-97 described in -160185 are advantageously selected, but the present invention is not limited thereto.

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 IV on page IV or the aforementioned JP-B-49-25500,
43-4933, JP-A-59-19032, and 59-19032.
192242.

The sensitizing dyes used in the present invention may be used in combination of two or more. 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. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025 and the like, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-5-102733 and JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion.
As disclosed in Japanese Patent No. 74624, a method of dissolving a dye using a compound that causes 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 used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion 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 the specifications of JP-A No. 60-196,749, the start of chemical ripening during the step of forming silver halide grains and / or before desalting, during and / or after desalting. Previous period, Japanese Patent Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A No. 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, during the chemical ripening step, or when the chemical ripening is completed. May be added separately, such as before or after chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be added and divided. Good.

The addition 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. And 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. 0.5 × 10 ^{-7 to} 2.0 × 10 ^-6
A molar addition amount is more preferred.

The support used in the present invention includes, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
Glass plate, cellulose acetate, cellulose nitrate, for example, polyester film such as polyethylene terephthalate, JP-A-7-234478, and US
A support comprising a styrenic polymer having a syndiotactic structure described in JP-A-5,558,979;
-538, US4,645,731, US4,93
Examples of the support include a polyester film described in JP-A-3,267 and SU4,954,430 coated with a vinylidene chloride copolymer. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

As the binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, gelatin is preferably used, but polymers described in paragraph No. 0025 of JP-A-10-268644 can also be used. The coating amount of the binder is such that the amount of the binder 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 silver halide emulsion The total amount of binder in the total hydrophilic colloid layer on the side having the layer and the total hydrophilic colloid layer on the opposite side is 7.
0 g / m ² or less, preferably 2.0 to 7.0 g / m ²
m ² .

In the present invention, in order to control the surface roughness of the outermost layer surface of the silver halide light-sensitive material, fine particles of inorganic and / or organic polymer (hereinafter referred to as a matting agent) are contained in a hydrophilic colloid layer. ) Is used. The surface roughness of the outermost layer surface of the light-sensitive material having the silver halide emulsion layer and the outermost layer surface opposite to the emulsion layer should be controlled by variously changing the average particle size and the amount of the matting agent. Can be. The layer containing the matting agent may be any layer of the light-sensitive material constituting layer, but the side having the silver halide emulsion layer is preferably contained in a layer farther from the support to prevent pinholes, particularly The outermost layer is preferred.

The matting agent used in the present invention may be any solid particles which do not adversely affect the photographic characteristics. Specifically, Japanese Patent Application Laid-Open No. 10-26846
No. 4, paragraphs [0009] to [0013]. The average particle size of the preferred matting agent in the present invention,
It is 20 μm or less, particularly in the range of 1 to 10 μm.
In the present invention, the preferable addition amount of the matting agent is 5 to 40.
0 mg / m ^2, in particular from 10 to 200 mg / m ^2. The surface roughness of the light-sensitive material of the present invention is such that at least one of the surface having the emulsion layer and the outermost layer surface opposite thereto, preferably both have a Bekk smoothness of 4000 seconds or less,
More preferably, it is 10 seconds to 4000 seconds. The Beck smoothness is determined by Japanese Industrial Standard (JIS) P8119 and TAP
It can be easily obtained by the PI standard method T479.

In the present invention, the matting agent sinks during coating and drying of the silver halide light-sensitive material, or the pressure increase or decrease in handling during automatic conveyance, exposure, development and the like.
Colloidal inorganic particles can be used in a silver halide emulsion layer, an intermediate layer, a protective layer, a back layer, a back protective layer, and the like for the purpose of improving curl balance, scratch resistance, and adhesion resistance. Preferred colloidal inorganic particles include JP-A-10-268644, paragraphs 0008 and 0014.
The described elongated silica particles, colloidal silica, and pearl-like (pearl necklace-shaped) colloidal silica manufactured by Nissan Chemical Industries, Ltd .: “Snowtex-PS” and the like.

The amount of the colloidal inorganic particles used in the present invention is 0.01 to 2.0, preferably 0.1 to 0.1 in terms of dry weight ratio to the binder (eg, gelatin) of the layer to be added. -0.6.

In the present invention, a polyhydroxybenzene compound described in JP-A-3-39948, page 10, lower right line, line 11 to page 12, lower left line, line 5 is used for the purpose of improving the sense of pressure increase and decrease. Is preferred. In particular,
Compounds of the compounds (III) -1 to 25 described in the publication.

In the present invention, a polymer latex can be used for the purpose of improving the brittleness, the dimensional stability, the feeling of pressure change, and the like. As the polymer latex, U.S. Pat. Nos. 2,763,652, 2,852,382, JP-A-64-538, JP-A-62-115152, JP-A-5-66512, JP-A-5-80449, Tokiko Sho 60-
No. 15935, No. 6-64058 and No. 5-450
Polymer latexes composed of various monomers such as alkyl acrylates and alkyl methacrylates described in JP-B No. 14 and No. Sho.
7, JP-A-50-73625, JP-A-7-1521
12, a polymer latex copolymerized with a monomer having an active methylene group and a monomer such as an alkyl acrylate described in JP-A-8-137060. Particularly preferably, JP-A-8-248548,
It is a polymer latex having a core / shell structure having a repeating unit composed of an ethylenically unsaturated monomer having an active methylene group in a shell portion described in JP-A-8-208767 and JP-A-8-220669. Polymer latexes having a core / shell structure having an active methylene group in the shell portion do not decrease the wet film strength of the photographic light-sensitive material, and are difficult to adhere such as brittleness, dimensional stability, and photosensitive materials. And the latex itself has improved shear stability. The amount of the polymer latex to be used is 0.01 to 4.0, preferably 0.1 to 2.0 in terms of dry weight ratio to the binder (eg, gelatin) of the layer to be added.

In the present invention, in order to lower the pH of the coating film for the purpose of improving the storage stability of the silver halide light-sensitive material and improving the sensitivity to pressure fluctuation, the same method as described in JP-A-7-104413, page 14, left line 1 is used. It is preferable to use the acidic polymer latex described on line 30 on the right side of the page. Specifically, compounds II-1) to II-9) described on page 15 of the publication. JP-A-2-103
No. 536, page 18, lower right, line 6 to page 19, upper left, first line, compounds having an acid group. The pH of the coating film on the side having the silver halide emulsion layer is preferably from 6 to 4.

In the present invention, at least one of the constituent layers of the silver halide light-sensitive material has a surface resistivity of 25 ° C. and 25%.
It can have a conductive layer of 10 ¹² Ω or less in an atmosphere of RH. As the conductive substance used in the present invention,
Conductive substances described in JP-A-2-18542, page 2, lower left, line 13 to page 3, upper right, line 7; Specifically, the metal oxide described in the second page from the lower right line on page 2 to the 10th lower right line in the same publication, and the compounds P-1 to P-1 described in the same publication
A conductive polymer compound of P-7. USP5,575,95
7, paragraph No. 0034-0 of JP-A-10-142938
043, JP-A-11-223901, paragraph number 0013
To 0019 can be used.

In the present invention, in addition to the above-mentioned conductive material, JP-A-2-18542, page 4, upper right, second line to page 4, lower right, lower third line; A better antistatic property can be obtained by using the fluorine-containing surfactant described in the sixth line from the lower left of the page to the fifth line on the lower right of the page 13 of the publication.

In the present invention, the silver halide emulsion layer or other hydrophilic colloid layer may contain a coating aid, an additive dispersing / solubilizing agent, improvement of lubricity, prevention of adhesion and improvement of photographic properties (for example, development acceleration). Various surfactants can be used for the purpose of, for example, high contrast, sensitization, and storage stability). For example, surfactants described in JP-A-2-12236, page 9, upper right line, line 7 to lower right line, line 3 of the same page. JP-A-2-103
No. 536, page 18, lower left line, line 4 to lower left line, line 7, the PEG surfactant. Specifically, compounds VI-1 to VI-15 described in the publication. JP-A-2-1854
No. 2, page 4, upper right, line 2 to page 4, lower right, lower third line; JP-A-3-39948, page 12, lower left, line 6 to page 13, lower right, line 5 Fluorinated surfactant.

In the present invention, various slip agents can be used for the purpose of improving the transportability of the silver halide light-sensitive material in an automatic transporter, the scratch resistance, and the pressure sensitivity characteristics.
For example, JP-A-2-103536, page 19, upper left 1
From the fifth line to the upper right line on page 19 of the publication, JP-A-4-21
No. 4,551, paragraph Nos. 0006 to 0031.

In the present invention, compounds described in JP-A-2-103536, page 19, upper left, line 12 to page 19, upper right, line 15 are contained as plasticizers for the coating film of the silver halide photosensitive material. be able to.

In the present invention, as a crosslinking agent for a hydrophilic binder, from page 5, line 18, upper right line to line 17, upper right line, JP-A-2-103536, JP-A-5-297508
The compounds described in paragraphs [0008] to [0011] can be used. 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 5
The range is preferably from 0 to 200%, more preferably from 70 to 200%.
The range is 180%. The swelling ratio of the hydrophilic colloid layer is
The thickness (d0) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic light-sensitive material was measured, and the silver halide photographic light-sensitive material was immersed in distilled water at 25 ° C. for 1 minute to swell. (△ d) was measured and the swelling ratio (%) = △
It is determined by the formula of d ÷ d0 × 100.

In the present invention, the drying, drying and winding up in a roll after drying of the silver halide light-sensitive material are described in JP-A-10-26.
It is preferably carried out by the method described in paragraph number 0026 to 0032 of No. 8464.

In the present invention, it is preferred that the coated photosensitive material is subjected to heat treatment at any time from coating to development. The heat treatment may be performed continuously immediately after the application or after a certain period has elapsed, but it is preferable to start the heat treatment within a short period, for example, within one day. The heat treatment is mainly for accelerating the hardening reaction to obtain a film strength that can withstand the development process, and the heat treatment conditions are appropriately determined according to the type of the hardener, the amount added, the film pH, the required film strength, etc. Although it has to be determined, it is preferably from 30 to 60C, more preferably from 35C to 50C. The period of the heat treatment is preferably 30 minutes to 10 days.

In the present invention, it is preferable that the nucleating agent contains at least one hydrazine derivative represented by the general formula (D). General formula (D)

[0067]

Embedded image

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—, and —PO (R ₃₀ ) — groups (R ₃₀ is R ₁₀
Selected from the same range as defined groups, it may be different from R _10. ) Or iminomethylene group.
A ₁₀ and A ₂₀ are both a hydrogen atom, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group;
Or a substituted or unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group.

In the formula (D), 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. is there. In the general formula (D), R ₂₀
Is an aryl group of a single ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring. R
_{As the} heterocyclic group represented by ₂₀ , a monocyclic or condensed ring, saturated or unsaturated, aromatic or non-aromatic heterocyclic group, for example, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, Examples include a quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, piperidine ring, and triazine ring. Preferred as R ₂₀ is an aryl group, and particularly preferred is a phenyl group.

The group represented by R ₂₀ may be substituted. Representative substituents include, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group) , An active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (eg, a pyridinio group), an acyl group, an alkoxycarbonyl group, an 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 (ethyleneoxy group Or contain propyleneoxy group units repeatedly ), 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, an (alkyl, aryl, or heterocyclic) amino group, N -Substituted nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, isothioureido group, imide group, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Grade ammonium, oxamoylamino, (alkyl or aryl) sulfonyluureido, acylureido, N-acylsulfamoylamino, nitro, mercapto, (alkyl, aryl, or heterocycle) thio, An alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an N-acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a phosphate amide or a phosphate ester structure. Groups, and the like. These substituents may be further substituted with these substituents.

The substituent which R ₂₀ may have is preferably an alkyl group having 1 to 30 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 (D), 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, methanesulfonamidomethyl group, benzenesulfonamidomethyl group,
Examples include a hydroxymethyl group, a methoxymethyl group, a methylthiomethyl group, a phenylsulfonylmethyl group, an o-hydroxybenzyl group, and the like. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, and examples thereof include a vinyl group, a 2,2-dicyanovinyl group, a 2-ethoxycarbonylvinyl group, and a 2-trifluoro-2-methoxycarbonylvinyl group. . 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. Examples include a phenyl group, a 3,5-dichlorophenyl group, a 2-methanesulfonamidophenyl group, a 2-carbamoylphenyl group, a 4-cyanophenyl group, and a 2-hydroxymethylphenyl group. Preferably, the heterocyclic group is a 5- to 6-membered, saturated or unsaturated, containing at least one nitrogen, oxygen, and sulfur atom.
It may be a monocyclic or condensed-ring heterocyclic group and may be a heterocyclic group containing a quaternized nitrogen atom, such as a morpholino group, a piperidino group (N-substituted), a piperazino group, an imidazolyl group, an indazolyl group ( 4-nitroindazolyl group, pyrazolyl group, triazolyl group, benzimidazolyl group, tetrazolyl group, pyridyl group, pyridinio group (N-methyl-3-pyridinio group, etc.), quinolinio group,
And a quinolyl group. Morpholino group, piperidino group,
A pyridyl group, a pyridinio group and the like are particularly preferred.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, such as 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 and 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 substituents include those exemplified as the substituents for R ₂₀ .

In the general formula (D), R ₁₀ is G ₁₀ -R ₁₀
The portion to divide the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁₀ -R ₁₀ parts of atoms, examples of which include for example, JP 63-29751 and the like.

The hydrazine derivative represented by the formula (D) may have a built-in adsorptive group that adsorbs to silver halide. Examples of such an adsorbing group include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups, which are described in U.S. Pat. Nos. 4,385,108 and 4,459,347; Nos. 195233, 59-200231, 59-201045, 59-201046, and 5
Nos. 9-201047, 59-201048, 59
JP-201049, JP-A-61-170733, and JP-A-61-170933.
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, JP-A-2-285
No. 344.

R ₁₀ or R _{20 in} the formula (D) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. In the present invention, the ballast group means a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), alkylamino group (or alkyleneamino group), alkylthio group having 6 or more carbon atoms. A group or a group having these as a partial structure, more preferably a linear or branched alkyl group (or alkylene group) having 7 or more and 24 or less carbon atoms, an alkoxy group (or an alkyleneoxy group), It represents an alkylamino group (or an alkyleneamino group), an alkylthio group, or a group having these as a partial structure. Examples of the polymer include those described in JP-A-1-100530.

R ₁₀ or R ₂₀ in the general formula (D) may contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the general formula (D) is a polymer having a hydrazino group. Specifically, for example, Japanese Patent Application Laid-Open No. 64-86
No. 134, JP-A-4-16938, JP-A-5-197
No.091, WO95-32452, WO95-324
No. 53, JP-A-9-179229, JP-A-9-235
264, JP-A-9-235265, JP-A-9-23
Compounds described in JP-A No. 5266 and JP-A-9-235267 are exemplified.

In the general formula (D), R ₁₀ or R ₂₀ represents a cationic group (specifically, a group containing a quaternary ammonium group, a group containing a quaternized phosphorus atom, or A quaternized nitrogen-containing heterocyclic group containing a nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, a (alkyl, aryl, or heterocyclic) thio group, or a dissociative group (alkaline Groups or partial structures having low acidity protons that can be dissociated in the developer,
Alternatively it means a salt thereof, specifically, for example, carboxyl group / -COOH, sulfo group / -SO ₃ H, a phosphonic acid group / -PO ₃ H, phosphoric acid group / -OPO ₃ H, hydroxy group / - OH group, a mercapto group / -SH, -SO ₂ NH ₂
Group, N-substituted sulfonamide group / —SO ₂ NH— group,
—CONHSO ₂ — group, —CONHSO ₂ NH— group, —N
HCONHSO ₂ — group, —SO ₂ NHSO ₂ — group, —CO
An NHCO- group, an active methylene group, an -NH- group inherent in a nitrogen-containing heterocyclic group, or a salt thereof). Examples of those groups include, for example, JP-A-7-234471, 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-7-259.
No. 240, JP-A-7-5610, JP-A-7-2443
No. 48, German Patent No. 4006032, JP-A-11-709
No. 3 and the like.

[0081] Formula (D) A _10, A ₂₀ at the hydrogen atom, of 20 or less alkyl or arylsulfonyl group (preferably a phenylsulfonyl group carbon, or the sum of the Hammett substituent constant -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, particularly preferred hydrazine derivatives in the present invention will be described. R ₂₀ is particularly preferably a substituted phenyl group. Examples of the substituent include a sulfonamide group, an acylamino group, an ureido group, a carbamoyl group, a thioureido group, an isothioureido group, a sulfamoylamino group,
-Acylsulfamoylamino group and the like are particularly preferred, furthermore a sulfonamide group and a ureido group are preferred, and a sulfonamide group is most preferred. The hydrazine derivative represented by the general formula (D) has a substituent at R ₂₀ or R ₁₀
Directly or indirectly, a ballast group, an adsorption group to silver halide, a group containing a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, or a group containing a repeating unit of an ethyleneoxy group , (alkyl, aryl or heterocyclic) thio group, an alkali dissociative group capable of dissociation by developing solution or hydrazino group (group represented by -NHNH-G ₁₀ -R ₁₀ capable of forming a multimer, It is particularly preferred that at least one of) is substituted. Moreover,
As the substituent of R _20, directly or indirectly, preferably have any one group described above, most preferably represents a phenyl group R ₂₀ is substituted by a benzene sulfonamide group, the sulfonic This is the case where any one of the aforementioned groups is directly or indirectly substituted as a substituent on the benzene ring of the amide group.

Among the groups represented by R ₁₀ , preferred are
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, more preferably a hydrogen atom, an alkyl group, or a substituted aryl group (an electron-withdrawing group or an o-hydroxymethyl group is particularly preferred as the substituent); Most preferably, it is a hydrogen atom or an alkyl group. Alkoxy group in the case of G ₁₀ is -COCO- group, an aryloxy group is preferably an amino group, a substituted amino group, specifically an alkylamino group, an arylamino group or heterocyclic amino group of a saturated or unsaturated, preferably . Also G ₁₀
Is a —SO ₂ — group, R ₁₀ is preferably an alkyl group, an aryl group or a substituted amino group.

In the general formula (D), 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 (D) are shown below. However, the present invention is not limited to the following compounds.

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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

(Chemical 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. JP-A-9-22082, which is a compound 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. , A compound represented by the general formula (B), the general formula (C), the general formula (D), the general formula (E), or the general formula (F), specifically, the compound N-1 described in the same publication. ~ N-30. JP-A-9-2
A compound represented by the general formula (1) described in No. 2082,
Specifically, compounds D-1 to D-55 described in the publication. In addition, WO95-32452, WO95-32453
JP-A-9-179229, JP-A-9-23526
4, JP-A-9-235265, JP-A-9-2352
No. 66, JP-A-9-235267, JP-A-9-319
019, JP-A-9-319020, JP-A-10-1
No. 30275, JP-A-11-7093, JP-A-6-3
No. 32096, JP-A-7-209789, JP-A-8-208
No. 6193, JP-A-8-248549, JP-A-8-2
48550, JP-A-8-262609, JP-A-8-262609
JP-A-314044, JP-A-8-328184, JP-A-9
-80667, JP-A-9-127632, JP-A-9-127
-146208, JP-A-9-160156, JP-A-10-161260, JP-A-10-221800,
JP-A-10-213871, JP-A-10-25408
2, JP-A-10-254088, JP-A-7-120
864, JP-A-7-244348, JP-A-7-33
3773, JP-A-8-36232, JP-A-8-36
No. 233, JP-A-8-36234, JP-A-8-362
No. 35, JP-A-8-272022, JP-A-9-220
No. 83, JP-A-9-22084, JP-A-9-5438
No. 1 and JP-A-10-175946.

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

In the present invention, the hydrazine-based nucleating agent may be added to the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support, or to any of the other hydrophilic colloid layers. It is preferable to add to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. Also, two or more hydrazine-based nucleating agents can be used in combination. In the present invention, the added amount of the nucleating agent is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, and more preferably 2 × 10 ⁻⁵ mol per mol of silver halide.
X10 ^{-5 to} 5 × 10 ^-3 mol is most preferred.

In the present invention, it is preferable to incorporate an amine derivative, an onium salt, a disulfide derivative or a hydroxymethyl derivative as a nucleation promoting agent in the light-sensitive material. Examples of the nucleation accelerator used in the present invention are listed. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically compound A described in pages 49 to 58
-1) to A-73). 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 general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, compounds of Na-1 to Na-22 described on pages 16 to 20 of the same publication And compounds of Nb-1 to Nb-12. JP-A-8-2
General formula (1), General formula (2), General formula (3), General formula (4), General formula (5), General formula (6) and General formula (7) described in 72023 Compounds, specifically, compounds 1-1 to 1-19 described in the same specification, 2-
1-2-2, 3-1-3-36, 4
Compounds of -1 to 4-5, compounds of 5-1 to 5-41, 6
-1 to 6-58, and 7-1 to 7-38. JP-A-9-297377, p55, column 10
The nucleation promoting agent described in line 8 to line 8 to p69, column 44, line 44.

Specific examples of the nucleation accelerator used in the present invention are shown below. However, the present invention is not limited to the following compounds.

[0103]

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[0104]

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The nucleation promoting agent 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, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. A product 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 accelerator of the present invention may be added to any layer of the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support or any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleation accelerator of the present invention is 1 × 10 ⁻⁶ to 2 × per mol of silver halide.
10 ⁻² mol is preferred, 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferred, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is most preferred. Further, two or more nucleation accelerators can be used in combination.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right line, page 11 to page 12, lower left line, line 5. Specifically, compounds (III) -1 to 25 described in the same gazette.

Compounds represented by the general formula (I) described in JP-A-1-11832 and having substantially no absorption maximum in the visible region. Specifically, compound I-
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.

The polymer latex described in JP-A-2-103536, page 18, lower left line, line 12 to lower left line, line 20. A polymer latex having an active methylene group represented by the general formula (I) described in JP-A-9-179228, specifically, compounds I-1 to I-
I-16. Polymer latex having a core / shell structure described in JP-A-9-179228, specifically, compounds P-1 to P-55 described in the same specification. JP-A-7-1
An acidic polymer latex described on page 14, left line 1 to page 30, right line of JP-A-04413, specifically, compounds II-1) to II-9) described on page 15 of the same.

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 formula (FA), formula (FA1), formula (FA2) and formula (FA3) described in JP-A-7-179243. Specifically, compounds F1 to F34 described in the publication, JP-A-7-152112
Nos. (II-2) to (II-24) described in JP-A-7-1521
No. 12, (III-5) to (III-18), JP-A-7-15
(IV-2) to (IV-7) described in No. 2112. JP-A-2-
Solid disperse dyes described in JP-A-294638 and JP-A-5-11382.

JP-A-2-12236, page 9, upper right 7
The surfactant described in the third line from the line on the lower right side of the same page. JP 2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; 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 VI-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.

JP-A-2-18542, page 3, lower right 1
The binder described in the second to 20th lines.

Next, the compound represented by formula (I) will be described in detail. General formula (I)

[0122]

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In the formula, Y and Z may be the same or different.
N or CR_Two (R_Two Represents an alkyl group or an aryl group.
S), R₁ Is -SO_ThreeM, -COOM, -OH, -NH
SO_TwoR _Three, -SO_Two NR_Three R_Four And -NR_Five CONR
_Three R_Four Substituted with at least one member selected from the group consisting of
Alkyl, aryl or heterocyclic groups or
An alkyl group, an aryl group or a heterocyclic group via a linking group
Represents a group constituted by R_Three , R_Four And R_Five Is the same
May be one or different, and each is a hydrogen atom or a carbon number of 1-4.
Represents a lower alkyl group. M is a hydrogen atom, alkali gold
Represents the genus, quaternary ammonium and quaternary phosphonium.

Specific examples of the alkyl group represented by R ₁ include a linear, branched or cycloalkyl group having 1 to 20 carbon atoms (eg, methyl, propyl, hexyl, dodecyl, isopropyl, etc.). Specific examples of the cycloalkyl group having 1 to 20 carbon atoms (for example, cyclopropyl group, cyclohexyl group and the like) and the aryl group include 6 to 2 carbon atoms.
0 aryl groups (for example, phenyl group, naphthyl group, etc.),
The heterocyclic group is specifically one or more nitrogen, oxygen, or a seven-membered heterocyclic ring, and further includes those forming a condensed ring at an appropriate position (for example, a pyridine ring, a quinoline ring, Pyrimidine ring, isoquinoline ring, etc.).
Further, the alkyl group, the aryl group and the heterocyclic group may be further substituted with substituents other than those listed above, specifically, a halogen atom (F, Cl, Br, etc.), an alkyl group (methyl group, ethyl Group), aryl group (phenyl group,
p-chlorophenyl group and the like) alkoxy group (methoxy group,
Methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, Benzamide group), alkoxycarbonylamino group (methoxycarbonylamino group, etc.),
Aryloxycarbonylamino group (phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, nitro group, amino group (unsubstituted amino group, dimethylamino Group), an alkylsulfinyl group (such as a methoxysulfinyl group), an arylsulfinyl group (such as a phenylsulfinyl group), an alkylthio group (such as a methylthio group), and an arylthio group (such as a phenylthio group). May be substituted two or more, and when substituted two or more, they may be the same or different. The above-mentioned linking group that may be included in R ₁ includes —S—, —O—, and —N (R ₃ )
-, - CO -, - SO -, - SO 2 -, - SO 2 N (R 3
_{) -, - CON (R 3} ) -, - COO- is preferred.
Here, R ₃ has the same meaning as the above-described —NHSO ₂ R _{3 and the} like.

Specific examples of R ₁ having a linking group include the following.

[0126]

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The alkyl group and the aryl group represented by R ₂ each include those having a substituent, and examples of the substituent include the same substituents as those of R ₁ .

Among the compounds represented by the general formula (I), those represented by the general formula (II) are particularly preferable. General formula (II)

[0129]

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R _{5 in the} general formula (II) has at least one —C
_{OOM, -SO 3 M, -OH,} -NHSO 2 R 3, -S
Represents a phenyl group substituted with O ₂ NR ₃ R ₄ or —NR ₃ CONR ₃ R ₄ , and the phenyl group may be further substituted with another substituent. Where -COO
_{M, -SO 3 M, -OH,} -NHSO 2 R 3, -SO 2
When there are two or more NR ₃ R ₄ and —NR ₃ CONR ₃ R _4, they may be the same or different, and —COOM, —
SO ₃ M is particularly preferred. M has the same meaning as that represented by the general formula (I). Hereinafter, specific examples of the compound represented by formula (I) used in the present invention will be shown, but the scope of the present invention is not limited to this compound.

[0131]

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[0132]

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[0133]

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[0134]

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The compound represented by the general formula (I) can be easily synthesized by using isothiocyanate as a starting material, as is generally well known. Patents in which the following synthetic methods are described;
Write the literature. U.S. Pat. Nos. 2,585,388 and 2,5
41,924, JP-B-42-21842, U.S. Pat. No. 3,266,897, British Patent 1,275,701
No., JP-A-56-111846, DA Berges et a
l., "Journal of Heterocyclic Chemistry" Vol.15 No.981
(1978), "The Chemistry of Heterocyclic Chemis
try "Imidazoleand Derivatives part I, 336-339
Chemical Abstract 58, 7921 (1963), p. 394, E.
Hoggarth "Journal of Chemical Society" 1949,
1160-1167, by SR Sandler W. Karo "Organic
Functional Group Preparation "Academic Press (1
968), pp. 312-315, II Kovtunovskaya Lovshine
Written by Tr.Ukr.Inst.Eksperim Endokrinol 18: 345 (19
61), M. Chamdon et al., Bull.Chem. Fr., 723 (1954),
DA Shirley, DW Alley, J. Amer. Chem. Soc., 79, 49
22 (1957), A. Wohl, w. Marckwald, German Chemical Society (B
er.) 22, 568 (1889). The compound represented by the general formula (I) is used in an amount equivalent to that of a usual additive, but is preferably 5 mg to 1 g / liter, more preferably 10 mg / l.
Used at ~ 500 mg / liter.

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 dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonates, and may be used alone or in combination. In particular, it is preferable to contain a dihydroxybenzene-based developing agent and an auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene-based developing agent. Examples include a combination of an ascorbic acid derivative and a p-aminophenol. Examples of the developing agent used in the present invention include dihydroxybenzene developing agents such as hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred. Further, ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred from the viewpoint of material cost.

The developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 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- (N-methylamino) phenol, etc., among which N-methyl-p-aminophenol or JP-A-9-297377. And aminophenols described in JP-A-9-297378 are preferred.

The dihydroxybenzene-based developing agent is preferably used usually in an amount of 0.05 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 0.10 mol / l. It is preferably used in an amount of from 0.5 mol / l to less than 0.06 mol / l, preferably from 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is preferably used in an amount of usually 0.01 mol / l to 0.5 mol / l, preferably 0.05 mol / l to 0.5 mol / l.
0.3 mol / l is more preferred. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is used in an amount of 0.01 mol / liter or less.
It is preferable to use 0.5 mol / l, 1-phenyl-3-pyrazolidones or p-aminophenols in an amount of 0.005 mol / l to 0.2 mol / l.

The developer used 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,
Carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphorus Acid salts (eg, sodium salt, potassium salt) and the like are used, and preferably, carbonate and boric acid are used. The amount of buffer, especially carbonate used, is preferably 0.05 mol /
Liter or more, especially 0.08 to 1.0 mol / liter.

In the present invention, both the developing solution and the developing replenisher have the property that “the rise in pH when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.5 or less”. Is preferred. As a method for confirming that the developing solution or replenisher used has this property, the pH of the developing solution or replenisher to be tested is adjusted to 1
The solution was adjusted to 0.5, and then 0.1 mol of sodium hydroxide was added to 1 liter of the solution. The pH value of the solution at this time was measured. It is determined to have properties. In the present invention, it is particularly preferable to use a development start solution and a development replenisher whose rise in pH value in the above test is 0.4 or less.

The preservative used in the present invention includes sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. The sulfite is preferably at least 0.2 mol / l,
In particular, it is used in an amount of 0.3 mol / l or more, but if it is added in an excessively large amount, it causes silver contamination in the developing solution. Therefore, the upper limit is preferably 1.2 mol / l. Particularly preferably, it is 0.35 to 0.7 mol / liter. As the preservative of the dihydroxybenzene developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The addition amount is from 0.03 to 0.09 in molar ratio to the dihydroxybenzene-based developing agent.
The range of 0.12 is preferable, and particularly preferably 0.05 to
It is in the range of 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Examples of additives other than those described 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, 3-
(5-mercaptotetrazol-1-yl) sodium benzenesulfonate, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventing agents. In addition, mercapto compounds, indazole compounds, benzotriazole compounds, and benzimidazole compounds can be used as antifoggants or black pepper.
It may be included as an 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. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

Further, various organic and organic compounds are contained in the developing solution 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, acyelaic 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-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, etc.
Compounds described in 5-67747, 57-102624 and JP-B-53-40900 can be mentioned.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in US Pat. Nos. 3,214,454 and 3,794,591 and German Offenlegungsschrift 2,227,369, and Research Disclosure, Vol. 181, Item 18170 (1979). May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. Other examples include Research Disclosure 18170, JP-A-57-208554, and JP-A-57-208554.
4-61125, 55-29883, 56-973
47 and the like.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A-52-102726, JP-A-53-42730, JP-A-54-2127, JP-A-55-4024 and JP-A-55-40.
25, 55-126241, 55-65555, 55-65556, and the compounds described in Research Disclosure 18170 described above.

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 the developer.

Further, as a silver stain preventing agent in the developer,
For example, JP-A-56-24347, JP-B-56-465.
85, JP-B-62-2849, JP-A-4-36294
2. In addition to the compounds described in JP-A-8-6215, triazines having at least one mercapto group (for example,
-23830, JP-A-3-282457, JP-A-7-1
75178), pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4, 6
-Trimercaptopyrimidine, JP-A-9-274289
And the like pyridines (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 (for example, 2-mercaptopyrazine,
2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, and the like pyridazines (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimer Mercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177,
The polyoxyalkyl phosphonate described in U.S. Pat. No. 5,457,011 can be used. These silver stain inhibitors can be used alone or in combination of two or more, and the addition amount is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol, per liter of the developer.
Further, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, a color tone agent, a surfactant, an antifoaming agent, a hardener and the like may be contained as necessary.

The preferred pH of the developer is from 9.0 to 12.0.
And particularly preferably in the range of 9.0 to 11.0, more preferably in the range of 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 the cation of 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, it is preferable that the molar ratio of potassium ion and sodium ion in the developer is 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 replenishing amount of the developing solution is 390 ml or less, preferably 325 to 30 ml, and most preferably 250 to 120 ml per 1 m ² of the light-sensitive material. The development replenisher has the same composition and
It may have a concentration and / or a composition and / or concentration different from the starting solution.

As the fixing agent of the fixing 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 in 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, potassium 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 having a hardening agent and the like as separate parts, or may be a one-part composition containing all components.

If necessary, a preservative (for example, sulfite, bisulfite, 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 hydrogencarbonate, 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 aluminum stabilizing ability or water softening ability (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 salts and saccharides thereof in an amount of 0.001 mol / L to 0.5 mol / L, preferably 0.005 mol / L to 0.3 mol. / Liter), but it is better not to include a boron-based compound from the viewpoint of environmental protection in recent years.

In addition, compounds described in JP-A-62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing promoters and the like can be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and JP-A-57-6840.
The amphoteric surfactants described above can be used, and 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 JP-B-45-35754, JP-A-58-122535, and JP-A-58-1.
Thiourea derivatives described in 22536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. No. 4,126,459, JP-A-64-4739, JP-A-1
-4739, 1-159645 and 3-1017
28, a mesoionic compound described in 4-170539, and a thiocyanate.

The pH of the fixing solution in the present invention is preferably 4.0 or more, more preferably 4.5 to 6.0. The fixing solution is mixed with a developer to increase the pH due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for the hardened fixing solution, and 7.0 or less for the non-hardened fixing solution. Is 6.7 or less.

The replenishing amount of the fixing solution is 500 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml per 1 m ² of the photographic material. 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 the reproducing apparatus, there is, for example, FS-2000 manufactured by Fujifilm. Also, using an adsorption filter such as activated carbon,
It is also preferable to remove dyes and the like.

When the developing and fixing agent in the present invention is a liquid agent, it is preferable to store it in a packaging material having low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Even if the developing agent and the fixing agent in the present invention are solidified, the same result as that of the liquid agent can be obtained. However, the solid processing agent will be described below. As the solid preparation in the present invention, known forms (powder, granule, granule, lump, tablet, compactor, briquette, plate, stick, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

As the coating agent and granulation aid, known ones can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 48, line 48 to column 3, line 13 can be referred to.

In the case of forming a plurality of layers, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets, briquettes, or the like. It may be packaged in a similar layer configuration. These methods are described in, for example, JP-A-61-259921,
16841, 4-78848 and 5-93991.

The bulk density of the solid processing agent is 0.5 to 6.0 g.
/ Cm ³ is preferable, and particularly, the tablet is 1.0 to 5.0 g / c.
m ³ is preferred, and the granules are preferably 0.5 to 1.5 g / cm ³ .

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, JP-A-4-7884.
8, 5-93991, JP-A-4-85533, 4-
85534, 4-85535, 5-134362,
5-197070, 5-204098, 5-22
4361, 6-138604, 6-138605,
8-286329 and the like can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt solidification, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid preparation is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, Japanese Patent Laid-Open No. 6-242 is disclosed.
585 to 6-242588, 6-247432, 6-247448, 6-301189, 7-566
4. It is also preferable to make it foldable as disclosed in 7-5666 to 7-5669 in order to reduce the storage space of the waste packaging material. For these packaging materials, a screw cap, a pull-top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and the limitation is particularly limited. do not do. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a dissolving device having a dissolving portion and a portion for storing a completed solution as described in JP-A-9-80718. A method of dissolving and replenishing from a stock part, JP-A-5-119454,
6-19102 and 7-261357. A processing agent is introduced into a circulating system of an automatic developing machine as described in
There are a replenishing method, a method of adding and dissolving a processing agent in accordance with the processing of the photosensitive material in an automatic developing machine having a dissolution tank therein, and any other known methods can be used. The processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolution apparatus having an opening mechanism or an automatic developing machine as described in JP-A-9-138495. From the viewpoint of the latter, the latter is preferable. More specifically, a method of breaking through the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method described in JP-A-6-19102 and JP-A-6-9-9
5331.

The photosensitive material which has been developed and fixed is then washed or stabilized (hereinafter, unless otherwise specified, washing including the stabilization is performed. The liquid used for these is water or washing water. ). The water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing liquid. These replenishing amounts are generally 1 m ² of photosensitive material.
From about 17 liters to about 8 liters per volume, although lower replenishment rates can be used. 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 for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, 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. Various oxidizing agents (for example, 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.

As a method for reducing the replenishing amount of washing, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time, and the replenishing amount of washing is 200 to ⁵ per m ² of the photosensitive material.
0 ml is preferred. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished to a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, a scale preventing means may be provided in the washing step. As the scale prevention means, known means can be used, and there is no particular limitation, but a method of adding a sunscreen (a so-called scale inhibitor), a method of energizing, a method of irradiating ultraviolet rays or infrared rays or far infrared rays, There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of 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 at regular intervals in order to suppress the generation of resistant bacteria. As a water-saving scale device, an apparatus AC-1000 manufactured by Fuji Photo Film Co., Ltd. and AB-5 manufactured by Fuji Photo Film Co., Ltd. as a scale inhibitor may be used.
231485 may be used. 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 oxides (eg, 2-mercaptopyridine
-N-oxide, etc.) and may be used alone or in combination. As a method of energizing, Japanese Patent Application Laid-Open No. 3-224
685, 3-224687, 4-162280, 4
-18980 can be used.

In addition, a known water-soluble surfactant or antifoaming agent 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 washing step can be mixed 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 polymers that have an 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.
JP-A-132435, JP-A-1-102553, JP-A-46-4
A bath containing the compound described in 4446 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, a film pH regulator, a hardening agent, a bactericide, a deodorant, an alkanolamine or a surfactant may be used in this stabilizing bath. Agents can also be added.

Additives such as deterrent agents and stabilizers to be added to the washing and stabilizing baths can be solid agents as in the case of the above-mentioned developing and fixing agents.

It is preferable that the waste of the developing solution, the fixing solution, the washing water and the stabilizing solution used in the present invention is incinerated. These waste liquids are, for example, Japanese Patent Publication No. 7-83867, U.S. Pat.
It is also possible to condense or solidify with a concentrating device as described in S5, 439, 560, etc. before disposing.

To reduce the replenishment 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. No. 3,025,779 and U.S. Pat.
1 and the like, 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, the time from the start of processing to the time after drying (dry to dry) is preferably 25 to 160 seconds, and the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds.
Second, the temperature of each liquid is preferably 25 to 50 ° C, and 30 to 40 ° C.
C is preferred. The temperature and time of water washing are 0-50 ° C and 4
0 second or less is preferable. 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. Any known drying method can be used, and there is no particular limitation. However, hot air drying, JP-A-4-15534, JP-A-5-2256, and JP-A-5-28929 can be used.
4 includes heat roller drying and drying by far infrared rays, and a plurality of methods may be used in combination.

[0182]

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 750 ml water 20 g gelatin 20 g sodium chloride 3 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 10 mg citric acid 0.7 g 2 liquid water 300 ml silver nitrate 150 g 3 liquid water 300 ml chloride Sodium 38 g Potassium bromide 32 g Potassium hexachloroiridate (III) (0.005% by mass KCl 20% aqueous solution) 5 ml Ammonium hexachlororhodate (0.001% by mass NaCl 20% aqueous solution) 7 ml Hexachloroiridium (III) used for three liquids Potassium acid (0.005% by mass KCl 20% by mass aqueous solution) and ammonium hexachlororhodate (0.001% by mass NaCl 20% by mass aqueous solution) were prepared by powdering KCl 20% by mass aqueous solution, NaCl It was prepared by dissolving in a 20% by mass aqueous solution and heating at 40 ° C. for 120 minutes.

One solution kept at 38 ° C. and pH 4.5 was added with 2
The liquid and the three liquids were each added in an amount corresponding to 90% with stirring over a period of 20 minutes to form 0.16 μm core particles. Subsequently, the following liquids 4 and 5 were added over 8 minutes, and the remaining 10% of the liquids 2 and 3 were added over 2 minutes to grow to 0.21 μm. further,
0.15 g of potassium iodide was added and the mixture was aged for 5 minutes to complete the particle formation. Fourth liquid 100 ml Silver nitrate 50 g Five liquid 100 ml Sodium chloride 13 g Potassium bromide 11 g Yellow blood salt 5 mg After that, water was washed by flocculation according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated. (PH 3.
Then, about 3 liters of the supernatant was removed (first rinsing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing).
Repeat the same operation as the second washing one more time (third washing)
The washing and desalting process was completed. To the emulsion after washing and desalting, 45 g of gelatin was added to adjust the pH to 5.6 and pAg 7.5, and 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 15 mg of sodium thiosulfate and 10 mg of chloroauric acid were added. Chemical sensitization was performed to obtain the optimum sensitivity at
100 mg of 3,3a, 7-tetraazaindene, proxel as a preservative (trade name, ICI Co., Ltd.
100 mg). Finally, an average grain size of 0.22 μm containing 70 mol% of silver chloride and 0.08 mol% of silver iodide.
m, a silver iodochlorobromide cubic grain emulsion having a variation coefficient of 9% was obtained. (Finally, as an emulsion, pH = 5.7, pAg =
7.5, conductivity = 40 μS / m, density = 1.2 × 10 ³
kg / m ³ and viscosity = 50 mPa · s. )

Preparation of Emulsion B 1 solution water 750 ml gelatin 20 g sodium chloride 1 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 10 mg citric acid 0.7 g 2 solutions water 300 ml silver nitrate 150 g 3 solutions water 300 ml chloride Sodium 38 g Potassium bromide 32 g Potassium hexachloroiridate (III) (0.005 mass% KCl 20 mass% aqueous solution) 5 ml Ammonium hexachlororhodate (0.001 mass% NaCl 20 mass% aqueous solution) 15 ml Hexachloroiridium used for 3 liquids Powders of potassium (III) acid (0.005% by mass KCl 20% by mass aqueous solution) and ammonium hexachlororhodate (0.001% by mass NaCl 20% by mass aqueous solution) were each made of KCl 20% by mass water The solution was prepared by dissolving in a 20% by mass aqueous solution of NaCl and heating at 40 ° C. for 120 minutes.

One solution kept at 38 ° C. and pH 4.5 was added with 2
The liquid and the three liquids were each added in an amount corresponding to 90% with stirring over a period of 20 minutes to form 0.16 μm core particles. Thereafter, 500 mg of 1,3,3a, 7-tetraazaindene was added, followed by the following solution 4 and solution 5 over 8 minutes, and then the remaining 10% amount of solution 2 and solution 3 over 2 minutes. , 0.18 μm. Further, 0.15 g of potassium iodide was added and the mixture was aged for 5 minutes to complete the particle formation. 4th liquid 100ml Silver nitrate 50g 5th liquid 100ml Sodium chloride 13g Potassium bromide 11g Yellow blood salt 2mg Thereafter, water was washed by flocculation according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated. (PH 3.
Then, about 3 liters of the supernatant was removed (first rinsing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing).
Repeat the same operation as the second washing one more time (third washing)
The washing and desalting process was completed. To the emulsion after washing and desalting, 45 g of gelatin was added to adjust the pH to 5.6 and the pAg to 7.5, and 10 mg of sodium benzenethiosulfonate, 3 mg of sodium benzenethiosulfinate, 2 mg of triphenylphosphine selenide, and 1 mg of chloroauric acid were added. Plus 55
Chemical sensitization to obtain optimum sensitivity at 100 ° C, and 1,3,3a, 7-tetraazaindene 100m as a stabilizer
g, 100 mg of proxel as a preservative. Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.18 μm and a variation coefficient of 10% was obtained. (Finally, as an emulsion, pH
= 5.7, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 × 10 ³ kg / m ³ , and viscosity = 50 mPa · s. )

Preparation of non-photosensitive silver halide grains 1 liquid 1 liter of water 20 g of gelatin 20 g of sodium chloride 20 g of 1,3-dimethylimidazolidin-2-thione 20 mg 8 mg of sodium benzenethiosulfonate 2 liquids 400 ml of silver nitrate 100 g 3 liquids Water 400 ml Sodium chloride 13.5 g Potassium bromide 45.0 g Potassium hexachlorodimate (III) (0.001% by mass aqueous solution) 860 ml

Solution 1, solution 2 and solution 3 maintained at 70 ° C. and pH 4.5 were simultaneously added over 15 minutes while stirring.
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.

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated.
(PH was in the range of 3.2 ± 0.2) Next, about 3 liters of the supernatant liquid was removed (first water washing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing). The same operation as the second washing was repeated one more time (third washing) to complete the washing / desalting process. 45 g of gelatin was added to the emulsion after washing with water and desalting, pH 5.7, pAg
Was adjusted to 7.5, and phenoxyethanol was added as a preservative. Finally, it contained 30 mol% of average silver chloride and 0.08 mol% of silver iodide, and had an average particle diameter of 0.45 μm and a variation coefficient of 10%. A dispersion of cubic iodine iodochlorobromide cubic milk particles was obtained. (Finally, as an emulsion, pH = 5.7, pAg
= 7.5, conductivity = 40 μS / m, density = 1.3 × 10 ³
kg / m ³ and viscosity = 50 mPa · s. )

Preparation of non-photosensitive silver halide grains 1 solution 1 liter of water 1 liter gelatin 20 g potassium bromide 0.9 g citric acid 0.2 g NH ₄ NO ₃ 20 g hydrogen peroxide 3.5 g sodium benzenethiosulfonate 15 mg 2 solutions water 400 ml Silver nitrate 200 g 3 liquids Water 400 ml Potassium bromide 140.0 g Potassium hexachlorodium (III) (0.001% by mass aqueous solution) 4000 ml

While stirring one solution maintained at 60 ° C.,
40 ml of OH (1N) was added, and 0.7 g of an aqueous silver nitrate solution was further added. After that, 1 /
Add two each by the control double jet method over a period of 20 minutes while keeping the silver potential at +24 mV, and after physical ripening for 2 minutes, use the same control double jet method for the remaining half of the second and third solutions. For 20 minutes to form particles.

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated.
(PH was in the range of 3.2 ± 0.2) Next, about 3 liters of the supernatant liquid was removed (first water washing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing). The same operation as the second washing was repeated one more time (third washing) to complete the washing / desalting process. 45 g of gelatin was added to the emulsion after washing with water and desalting, pH 5.7, pAg
Was adjusted to 7.5, and phenoxyethanol was added as a preservative. Finally, it contained 30 mol% of average silver chloride and 0.08 mol% of silver iodide, and had an average particle diameter of 0.8 μm and a coefficient of variation of 10%. A dispersion of unripe silver bromide tetradecahedral milk particles was obtained. (Finally, as an emulsion, pH = 5.7, pAg =
7.5, conductivity = 40 μS / m, density = 1.3 × 10 ³ k
g / m ³ and viscosity = 50 mPa · s. )

[0192]

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Preparation of Coated Sample On a polyethylene terephthalate film support having both surfaces shown below, each having a moisture-proof layer containing vinylidene chloride, a UL layer / emulsion layer / protective layer lower layer / protective layer upper layer protective layer was formed. A sample was prepared by coating. The preparation method, application amount and application method of each layer are shown below. <Emulsion layer> Emulsion A and emulsion B were mixed at a ratio of 1: 2, and sensitizing dye (sd-1) 5.7 × 10 ^-4 mol / mol Ag
Was added for spectral sensitization. Furthermore, KBr 3.4 × 10
⁻⁴ mol / mol Ag, compound (Cpd-1) 2.0 × 10 ⁻⁴ mol / mol Ag, compound (Cpd-2) 2.0 × 10 ⁻⁴ mol / mol
The mol Ag and the compound (Cpd-3) 8.0 × 10 ^-4 mol / mol Ag were added and mixed well. Then, 1,3,3a, 7-
Tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / mol Ag, hydrazine nucleating agent (Cpd- 4) was 1.5 × 10 ⁻⁴ mol / mol Ag, the nucleation promoter (Cpd-5) was 6.0 × 10 ⁻⁴ mol / mol Ag, 2,4
-Dichloro-6-hydroxy-1,3,5-triazine sodium salt at 90 mg / m ² ,
% By mass of colloidal silica having a particle size of 10 μm, aqueous latex (aqL-6) of 100 mg / m ² , polyethyl acrylate latex of 150 mg / m ² , methyl acrylate and 2-acrylamide-2-methylpropanesulfonic acid sodium salt, and Acetoxyethyl methacrylate latex copolymer (weight ratio 88: 5: 7)
mg / m ² , core-shell type latex (core: styrene / butadiene copolymer (weight ratio 37/63), shell:
Styrene / 2-acetoxyethyl acrylate (weight ratio 84/16), core / shell ratio = 50/50)
mg / m ² , 4% by mass of gelatin (Cpd-7)
Was added, and the pH of the coating solution was adjusted to 5.6 using citric acid. Thus Ag3.4g / m ² The emulsion layer coating solution was prepared on the following support was coated to a gelatin 1.5 g / m ^2. <Protective Layer Upper Layer> Gelatin 0.3 g / m ² 3.5 μm average amorphous silica matting agent 25 mg / m ² Compound (Cpd-8) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm ( 30 mg / m ² compound (Cpd-9) 50 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² compound (Cpd-10) 20 mg / m ² compound (Cpd-11) manufactured by Nissan Chemical Industries, Ltd. 20 mg / m ² Preservative (Proxel (trade name, manufactured by ICI Co., Ltd.)) 1 mg / m ² <Protective layer lower layer> Gelatin 0.5 g / m ² Non-photosensitive silver halide grains or as shown in Table 2. Amount Compound (Cpd-12) 15 mg / m ² 1,5-Dihydroxy-2-benzaldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² Compound (Cpd-13) 3 mg / m ² Preservative (Proxel 1.5 mg / m ² <UL layer> Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (Cpd-7) 40 mg / m ² Compound (Cpd-14) 10 mg / m ² Preservative (Proxel) ) 1.5 mg / m ²

The viscosity of the coating solution for each layer was adjusted by adding a thickener represented by the following structure (Z).

[0195]

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[0196]

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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 (Cpd-15) 40 mg / m ² compound (Cpd-16) 20 mg / m ² compound (Cpd-17) 90 mg / m ² Compound (Cpd-18) 40 mg / m ² compounds (Cpd-19) 26 mg / m ² 1,3-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 (Cpd -7) 120 mg / m ² Calcium nitrate 20 mg / m ² Preservative (Proxel) 12 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 μm) 200 mg / m ² Preservative (Proxel) 0.3 mg / m ²

[0198]

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<Support> An undercoat first layer and a second layer of the following composition on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were applied.

<One layer of undercoat layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle diameter 3 μm) 0.05 g Compound (Cpd) -20) 0.20 g colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Industry Co., Ltd.) 0.12 g 100 g by adding water, and further adjusted to pH = 6 by adding 10% by mass of KOH. The coating solution was dried at a drying temperature of 180 ° C. for 2 minutes and the dry film thickness was 0.1 mm
It was applied so as to have a thickness of 9 μm.

<Second Layer of Undercoat Layer> Gelatin 1 g Methylcellulose 0.05 g Compound (Cpd-21) 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Proxel 3.5 × 10 ^-3 g Acetic acid 0.2 g Water was added and 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness became 0.1 μm.

[0202]

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<Coating method> On the support provided with the above-mentioned undercoat layer, four layers of an UL layer, an emulsion layer, a protective layer lower layer, and a protective layer upper layer were formed in order from the side closer to the support as the emulsion surface side. At the same time while adding the hardener liquid by the slide bead coater method while maintaining the temperature at ℃, the cold air set zone (5
° C), and from the side closer to the support opposite to the emulsion surface, from the side closer to the support, a conductive layer and a back layer are simultaneously coated in the order of a hardener solution by a curtain coater method and a cold air set zone ( 5 ° C.). At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the back surface side, it was conveyed in a non-contact state with a roller and other parts until winding up. The coating speed at this time was 200 m / min.

<Drying Conditions> After setting, the mixture was dried with a drying air at 30 ° C. until the mass ratio of water / gelatin became 800%.
After drying 200 to 200% with a dry air at 35 ° C and 30% RH, the air is directly applied, and 30 seconds after the surface temperature reaches 34 ° C (assuming the drying is completed), 48 ° C and 2% RH.
For 1 minute. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800%.
It takes 35 seconds from 0% to 5 seconds from 200% to the end of drying.

This photosensitive material is wound up at 25 ° C. and 55% RH.
Heat treatment was performed at 35 ° C. and 30% RH for 72 hours.
Next, after cutting at 25 ° C. and 55% RH and humidity-controlling at 25 ° C. and 50% RH for 8 hours in a barrier bag conditioned for 6 hours,
Sealed with cardboard conditioned at 50 ° C 50% RH for 2 hours,
The samples shown in Table 2 were prepared. For comparison, a sample not subjected to heat treatment after winding was also prepared. When the humidity inside the barrier bag was measured, it was 45%. The film surface pH on the emulsion layer side of the obtained sample was 5.5 to 5.8, and the film surface pH on the back side was 6.0 to 6.5. The absorption spectra on the emulsion layer side and the back layer side were as shown in FIG. For the measurement of the absorption spectrum, a spectrophotometer U-3500 manufactured by Hitachi, Ltd. was used, and a sample whose surface on the side opposite to the measurement surface was removed was placed in a φ200 integrating sphere set in a sample chamber. A measurement was made.

The evaluation was performed by the following method. [Evaluation of Optical Characteristics] The obtained sample was measured with a spectrophotometer U3500 manufactured by Hitachi, Ltd. to 900 to 950 nm.
Was measured. The measurement was performed by installing an integrating sphere in the light receiving portion of the spectrophotometer so that the transmitted light of the film could be integrated and measured using an integrating sphere. [Evaluation of Sensor Suitability] Samples were loaded into the following image setters, and an operation of actually performing exposure processing was performed to evaluate whether or not there was a sensor detection defect.・ Dolev450 manufactured by Nippon Cytex Co., Ltd. ・ F9000 manufactured by Fuji Photo Film Co., Ltd. ・ Lux setter RC56 manufactured by Fuji Photo Film Co., Ltd.
If the 00V sensor detection failure occurs, “NO FIL
An error such as "M" is displayed. [Evaluation of photographic properties] The obtained sample was exposed to xenon flash light having an emission time of 10 ^-6 seconds through an interference filter having a peak at 667 nm and a step wedge. Then, using a test developer A, B, C or D and a fixer (B) to which the compounds shown in Table 1 were added based on the developer (A) having the following formulation, an FG-680AG automatic developing machine (Fuji Photo The film was processed under a developing condition of 35 ° C. and 30 ″.

Developer (A) The composition per liter of the concentrated solution is shown. 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 Sodium erythorbrate 9.0 g Diethylene glycol 7.5 g pH10. 79 For use, the mother liquor was
The replenisher was diluted at a ratio of 3 parts of water with respect to 4 parts of the concentrated solution, and the pH of the replenisher was 10.62.

Fixer (B) Formulation The formula per 1 L of the concentrated solution is shown. Ammonium thiosulfate 360 g Ethylenediamine tetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90. 0 g Tartaric acid 8.7 g Sodium gluconate 5.1 g Aluminum sulfate 25.2 g pH 4.85 For use, dilute 2 parts of water to 1 part of the above concentrated liquid. The pH of the working solution is 4.8.

[0209]

[Table 1]

[Evaluation of Photographic Properties] The sensitivity was expressed as the relative sensitivity, with the reciprocal of the amount of exposure giving a density of 1.5 when treated with the new solution as 100, and the value after running as relative sensitivity. A relative value of 95 to 105 is desirable. [Evaluation of practical skill density] Using an image setter RC5600V manufactured by Fuji Photo Film Co., Ltd., a test step was output while changing the light amount at 175 lines / inch, and development processing was performed under the processing conditions described above. LV to be 50%
The _Dmax part at the time of exposure with the value was measured, and it was set as the practical density. Note that the net% and the actual skill concentration are Macbeth TD
904. [Evaluation of photographic properties with fatigue developer] The above developer (A) Table 1
Then, each of the film samples of 80% blackening per day is treated with 300 sheets of large total size while replenishing 50 cc of the use liquid per large total size (50.8 cm × 61 cm),
By performing this process continuously for 4 days, a large amount of film was processed to obtain a developer having a pH lowered to 10.2 and an increased bromine ion concentration. [Evaluation of development unevenness] The development unevenness was evaluated on a scale of 1 to 5, with no development unevenness occurring on the film after running, and 1 as a state where development unevenness occurred on one surface of the film. In the case of No. 4, development unevenness occurs on a very small portion of the film, but this is a practically acceptable level, but the case of 3 or less is not practical.

Using the above-mentioned fatigue developing solution, photographic properties, changes in practical density and development unevenness were evaluated.

[0212]

[Table 2]

From Table 2, it can be seen that a sample in which the transmittance is reduced by 5% or more by adding a non-photosensitive silver halide has good sensor suitability. The decrease in the density is large, and this is an area that poses a problem in practical use. Further, even if a sample having good suitability for a sensor is not treated with a developing solution to which the compound of the present invention is added, uneven development occurs and the commercial value is lost. It can be seen that the processing method using the light-sensitive material and the developing solution of the present invention achieves the suitability for the sensor, the practical density (> 4.5) with the fatigue developing solution, and the improvement of the development unevenness.

Example 2 The same experiment as in Example 1 was carried out on the following solid developer (C).
When the test was carried out using the liquid to which the above-mentioned product was added and the solid fixing agent (D), the sample having the constitution of the present invention showed good performance as in Example 1.

Formulation of solid developer (C) Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (raw powder) 63.0 g Sodium sulfite (raw powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) 40.0 g or less collectively briquetted Diethylenetriamine / pentaacetic acid 2.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g 2-mercaptobenzimidazole-5 -Sodium sulfonate 0.45 g 4- (N-carboxymethyl-N-methylamino) -2,6-dimercaptopyrimidine 0.2 g Sodium erythorbate 6.0 g Potassium bromide 6.6 g Dissolve this in water Make up to 1 liter. pH 10.65

Here, in the form of raw materials, raw powders were used as general industrial products, and beads of alkali metal salts were commercially available. When the raw material was in the form of a briquette, a plate-like material obtained by pressurizing and compressing using a briquetting machine was crushed and used. For minor components, each component was blended before briquetting. 10 liters of the above treating agent was filled in a foldable container made of high-density polyethylene, and the outlet was sealed with an aluminum seal. Dissolution and replenishment are described in JP-A-9-80718,
A dissolution replenisher with an automatic opening mechanism as disclosed in US Pat.

Formulation of solid fixing agent (D) Formulation A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (raw powder) 19.0 g Sodium metabisulfite (raw powder) 18.0 g Anhydrous sodium acetate (raw) Powder) 42.0 g Agent B (liquid) Ethylenediamine / tetraacetic acid / 2Na / dihydrate 0.03 g Tartaric acid 2.9 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make up to 50 ml. . The fixing solution (D) was prepared by dissolving the agent A and the agent B in water and adjusting the solution to 1 liter. pH was 4.8.

The ammonium thiosulfate (compact) was obtained by compressing and compressing a flake product prepared by a spray-drying method with a roller compactor and crushing it into irregular shaped chips of about 4 to 6 mm, and blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of both Agent A and Agent B were filled in a foldable container made of high-density polyethylene, and the outlet of Agent A was sealed with an aluminum seal. The mouth of the B agent container was sealed with a screw cap. For dissolving and replenishing, a dissolving and replenishing apparatus having an automatic opening mechanism disclosed in JP-A-9-80718 and JP-A-9-138495 was used.

Example 3 The following developer (E) was used instead of the developer (A) of Example 1.
The same experiment as in Example 1 was conducted using a liquid to which the substances shown in Table 1 were added. As in Example 1, the light-sensitive material having the structure of the present invention showed good performance.

The composition of the developer (E) per liter of the concentrated solution is shown below. Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75.0 g 5-methylbenzotriazole 0.25 g 4-hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 1.35 g 4- (N-carboxymethyl-N-methylamino) -2,6-dimercaptopyrimidine 0.3 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.45 g Sodium erythorbrate 9.0 g Diethylene glycol 60.0 g pH 10.7 Before use, dilute the concentrate at a ratio of 2 parts of water to 1 part of the concentrated solution. PH of working solution is 10.5

Example 4 In Examples 1 to 3, the developing temperature was 38 ° C. and the fixing temperature was 37.
When the processing was performed with the temperature set to 20 ° C. and the development time set to 20 seconds, the same results as in Examples 1 to 3 were obtained, and the effect of the present invention was not lost.

Embodiment 5 In Embodiments 1 to 4, the automatic machine was replaced by FG-680AS manufactured by the company.
, The same processing was performed with the photosensitive material transporting speed set to a linear speed of 1500 mm / min to obtain similar results.

Example 6 Lux setter RC-5600V manufactured by Fuji Photo Film Co., Ltd.
Instead of using FT-R5055 Image Setter FT-R5055 manufactured by Dainippon Screen Co., Ltd., Select Set 5000, Avantra 25, or AccuSet 1000, Dreb 45 manufactured by Cytex Corporation
0 or Dreb 800, Rhino 630 from Heidel, Quasar, Hercules Elite, or Signa Setter, or Laxel F-9000, or Panther Pro 62 from Prepress Co., Ltd. When the same evaluation as in Examples 1 to 5 was performed,
Similar effects were obtained with the sample of the present invention.

[Brief description of the drawings]

FIG. 1 shows absorption spectra of an emulsion layer side and a back layer side in Examples of the present invention.

[Explanation of symbols]

The vertical axis indicates absorbance (0.1 interval), and the horizontal axis is 350 nm.
From 950 to 950 nm. The solid line shows the absorption spectrum on the emulsion layer side, and the broken line shows the absorption spectrum on the back layer side.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/74 G03C 1/74 5/31 5/31

Claims (5)

[Claims] 1. At least one photosensitive silver halide milk
Support at least one silver halide emulsion layer containing
In the silver halide photographic light-sensitive material having on the body,
Silver halide emulsion layer or another hydrophilic colloid layer
Containing a non-photosensitive silver halide emulsion,
10 to 200 mg / m of silver halide in terms of silver²
Coating amount of the non-light-sensitive silver halide emulsion.
By squeezing, the wavelength of the photosensitive material from 900 nm to 950
silver halide photography whose transmittance in nm is reduced by 4% or more on average
True photosensitive material contains a compound represented by the following general formula (I)
And replenish the developing solution having a pH of 9.0 to 11.0 with the developing solution.
250ml / m²It is characterized by developing as
Of a photosensitive silver halide photographic light-sensitive material. General formula (I)Wherein Y and Z are N or CR_Two (R_Two Is an alkyl group or
Represents a reel group), R ₁ Is -SO_Three M, -COOM,-
OH, -NHSO_Two R_Three , -SO_Two NR_Three R_FourAnd-
NR_Five CONR_Three R_Four At least selected from the group consisting of
Also represents an alkyl group, an aryl group or
Terrorist ring group or alkyl group, aryl group or hetero ring
The group represents a group constituted via a linking group. R_Three , R_Four Passing
And R_Five Represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms
Represent. M is hydrogen atom, alkali metal atom, quaternary ammonium
And quaternary phosphonium. 2. The method for processing a light-sensitive silver halide photographic material according to claim 1, wherein the non-light-sensitive silver halide emulsion comprises silver halide having a silver bromide content of 80 mol% or more. 3. The method for processing a light-sensitive silver halide photographic material according to claim 1, which comprises two or more different light-sensitive silver halide emulsions. 4. The at least one photosensitive silver halide emulsion has an average grain size of 0.2 μm or less.
4. The method for processing a photosensitive silver halide photographic material described in 1. above. 5. The processing of a light-sensitive silver halide photographic material according to claim 1, wherein the silver halide emulsion layer or another hydrophilic colloid layer contains at least one hydrazine derivative. Method.