JPH1039446A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable rapid processing of the photosensitive material and to enhance its storage stability with the lapse of time by incorporating a specified N-containing heterocyclic compound having a water-soluble group but no mercapto group or the like in a hydrophilic colloidal layer. SOLUTION: The photosensitive material has at least hydrophilic colloidal layers including at least one silver halide emulsion layer on a support and this hydrophilic colloidal layer contains the N-containing 5- or 6-membered heterocyclic compound having at least one water-soluble group but not a mercapto group or a blocked mercapto group, and this compound is represented by the formula in which Het is an optionally substituted hetero ring having no mercapto group or no blocked mercapto group; J is a bonding group having a+1 valencies; Q is a water-soluble group; (n) is an integer of 0-5; and each of (m) and (a) is an integer of >=1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material and a processing method thereof.

[0002]

2. Description of the Related Art Recently, in the development processing of a silver halide light-sensitive material (hereinafter, also referred to as a light-sensitive material), it is required to shorten a processing time and to reduce a waste liquid accompanying the processing.

[0003] In order to shorten the processing time, it is advantageous to use silver chloride or silver chlorobromide emulsions having higher solubility than silver iodobromide emulsions, and it is more advantageous to make silver halide grains finer and flatter. It is known that

On the other hand, in order to reduce the waste liquid, it is desirable to increase the image density with a small amount of silver.
Tabular grains are also suitable in terms of sharpness, color sensitization efficiency and the like.

[0005] However, silver chlorobromide or silver chloride emulsions having excellent development processability often have the disadvantage that fog is increased compared to silver iodobromide emulsions. Japanese Patent Application Laid-Open No. Sho 57-57 using mercaptobenzimidazoles having a functional group
No. 14836 is disclosed. However, in this technique, the fog is sufficiently suppressed by long-term storage of the light-sensitive material, but on the other hand, the sensitivity is significantly reduced, particularly when the light-sensitive material is chemically sensitized with a selenium compound or a tellurium compound. And fog increased remarkably, and further improvement was desired.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which can be processed quickly, and which has excellent storage stability over time. That is.

[0007]

The object of the present invention has been solved by the following constitution.

(A) In a silver halide photographic material having a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, the hydrophilic colloid layer is blocked with a mercapto group or a mercapto group. 5 having no group and having at least one water-soluble group
A silver halide photographic light-sensitive material containing a 6-membered nitrogen-containing heterocyclic compound.

(B) The nitrogen-containing heterocyclic compound is a compound represented by the following general formula (1): (a)
The silver halide photographic light-sensitive material according to the above item.

[0010]

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(In the formula, Het represents a substituted or unsubstituted 5- or 6-membered nitrogen-containing heterocyclic ring having no mercapto group or a group in which the mercapto group is blocked as a substituent;
Represents an a + 1-valent linking group, and Q represents a water-soluble group. n represents an integer of 0 to 5, and m and a represent an integer of 1 or more. (C) The silver halide photographic material as described in (b), wherein the nitrogen-containing heterocyclic compound is a compound represented by the following general formula (2) or (3).

[0012]

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(In the formula (2), W represents an oxygen atom, a sulfur atom, a nitrogen atom, or —C (R ₁ ) (R ₂ ) —,
X represents a nitrogen atom or —C (R ₁ ) —. Z represents a group of atoms necessary for forming a mercapto group as a substituent or a substituted or unsubstituted 5- or 6-membered nitrogen-containing aromatic heterocycle having no blocked mercapto group. R ₁ and R ₂
Represents a hydrogen atom or a substituent other than a mercapto group or a group in which a mercapto group is blocked. J, Q, n and m have the same meanings as in the general formula (1). ) (In the formula (3),
P, V, Y and T each represent a hydrogen atom, a nitrogen atom, or —C (R ₁ ) (R ₂ ) —. R ₁ , R ₂ , J, Q, n,
m has the same meaning as in general formula (1). (D) The silver halide photographic material according to the above (a), (b) or (c), wherein two parallel main planes of silver halide grains have a (100) plane, and A silver halide photographic light-sensitive material comprising tabular silver halide grains having an average silver chloride content of 20 mol% or more.

(E) The silver halide photographic material according to any one of (a) to (d) above, which is chemically sensitized with a selenium and / or tellurium compound. Silver photographic photosensitive material.

(F) The halogenation according to any one of (a) to (e), wherein the amount of the hydrophilic binder on the support is from 1.0 g to 3.5 g / m ² . Silver photographic photosensitive material.

(G) The silver halide photographic material according to any one of (a) to (f), wherein the hydrophilic colloid layer contains a hydrazine compound. Photosensitive material.

(H) The silver halide photographic material as described in (g) above, wherein the hydrazine compound has a sulfonamide bond.

(I) A method for processing a silver halide photographic light-sensitive material, comprising processing the silver halide photographic light-sensitive material according to any one of the above (a) to (h).

(J) The method for processing a silver halide photographic light-sensitive material as described in (j), wherein the processing is carried out by an automatic developing machine in which the replenishing amount of a developing solution is not more than 15 ml per sheet.

(K) The method for processing a silver halide photographic light-sensitive material as described in item (i) or (j), wherein the processing is performed by an automatic processor having a total processing time of 10 to 30 seconds.

Hereinafter, the present invention will be described in detail.

The silver halide photographic light-sensitive material of the present invention is a 5- to 6-membered heterocyclic compound having at least one water-soluble group, wherein the silver halide emulsion does not have a mercapto group or a group in which a mercapto group is blocked. (Hereinafter referred to as the compound of the present invention). Here, preferred compounds of the present invention are compounds represented by the above general formula (1), and more preferably general formulas (2) or (3). Hereinafter, these compounds will be described in detail.

In the compounds represented by the general formulas (1), (2) and (3), the group in which the mercapto group is blocked refers to a group in which the blocking group can be cleaved into a mercapto group during development processing. Specific examples of the blocking group include an acyl group, a sulfonyl group, and a cyanoethyl group. Any 5- to 6-membered heterocycle of the compound of the present invention can be used, and specific examples include, for example, pyrrolidine, piperidine, morpholine, thiomorpholine, pyrrole, pyridine, pyrimidine, pyrazine, triazine, imidazole, pyrazole, Heterocycles such as oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole and the like and condensed rings with these benzene rings are also included (the same applies to Het in the general formula (1)).

The linking group represented by J in the general formulas (1) to (3) is specifically alkylene, arylene, heteroarylene, -SO _2- , -SO-, -O-, -S-,
—N (R ₃ ) — alone or in combination
Valence groups. Here, R ₃ represents an alkyl group, an aryl group, or a hydrogen atom. J is preferably arylene, most preferably phenylene. n is preferably 0 or 1.

The water-soluble group represented by Q in the general formulas (1) to (3) represents a group capable of being anionized in a developer, and specifically includes a sulfonamide group, a sulfamoyl group, and a phenolic hydroxyl group. , A carboxyl group, a sulfo group, and salts thereof. Preferred are a carboxyl group and a sulfo group. m and a are preferably 1 or 2.

In the general formula (2), 5 to Z
As the 6-membered nitrogen-containing aromatic heterocycle, any may be used, and preferably pyridine, pyrimidine, pyrazine,
Each ring of triazine, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole, and condensed rings with these benzene rings can be mentioned. Preferred are a triazole ring and a tetrazole ring.

In the general formula (2), W is an oxygen atom, a sulfur atom,
X represents a nitrogen atom or —C (R ₁ ) (R ₂ ) —, and X represents a nitrogen atom or —C (R ₁ ) —.

Specific examples of the substituent represented by R ₁ and R ₂ include a halogen atom (a chlorine atom, a bromine atom, etc.) and an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethyl group) , Trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p
-Chlorophenyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.), cyano group, acylamino group (for example, acetylamino group, propionylamino Group, alkylthio group (eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3 -Methylureido, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamide group (dimethylsulfamoylamino group, etc.), carbamoyl group (for example, methylcarbamoyl group, ethylcarbamoyl group, dimethyl Carbamoyl group, etc. , A sulfamoyl group (e.g., ethyl sulfamoyl group, dimethylsulfamoyl group), an alkoxycarbonyl group (e.g. methoxycarbonyl group,
Ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl group (eg, back methanesulfonyl group, butanesulfonyl group,
Phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy group, nitro group, nitroso group, amine oxide group (For example, a pyridine-oxide group), an imide group (for example, a phthalimide group), a disulfide group (for example, a benzene disulfide group, a benzothiazolyl-2-disulfide group, etc.), a carboxyl group, a sulfo group, and a heterocyclic group (for example, a pyridyl group, a benzyl group) Imidazolyl group, benzothiazolyl group, benzoxazolyl group, etc.).

It is preferable that three of P, V, Y and T in the general formula (3) are N atoms, and in particular, P, V and Y
Is particularly preferably a nitrogen atom.

In the compounds represented by the general formulas (1) to (3),-(J) n- (Q) m of the heterocyclic ring may have a substituent at a position other than the above, Specific examples thereof include the above-mentioned substituents.

Hereinafter, specific examples of the compounds represented by formulas (1) to (3) of the present invention will be given, but the present invention is not limited to these.

[0032]

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[0033]

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The compounds represented by the general formulas (1) to (3) of the present invention can be easily synthesized by a method described in a known document such as Journal hua Plasticich Chemie [2], 124, 286. can do. The following compound (1)
An example of the synthesis of

<Synthesis Example> Synthesis of Exemplified Compound (1) 1- (4-carboxyphenyl) -tetrazole 4.5
g to 20 ml of methanol and 5 ml of concentrated aqueous ammonia.
To complete dissolution. Next, 2 ml of 35% aqueous hydrogen peroxide was added and the mixture was stirred at room temperature for 12 hours. Crystals precipitated after acidification by adding 1N hydrochloric acid were filtered and recrystallized from methanol to obtain 3.7 g of Exemplified Compound 1 (96% yield).

The above compound is a fog inhibitor for the silver halide photographic light-sensitive material of the present invention, and may be added at any time during the emulsion production process or during chemical ripening. If added before the completion of chemical ripening, the effect may be high, but if added separately before and after the completion, the effect may be further enhanced.

As the addition method, powder may be added as it is, or a solution dissolved in a low-boiling organic solvent such as methanol, ethanol, ethyl acetate or the like, water or a mixed solvent of a low-boiling organic solvent and water may be added. It does not matter. At this time, if necessary, a regulator for changing the pH may be used to enhance the solubility. Further, when added as an added particulate solid dispersion, an even higher effect may be obtained.

The amount of the compound to be added is 0.01 g to 0.5 g, preferably 0.02 g to 0.2 g, per mole of silver. In high silver chloride grains having an average silver chloride content of 20 mol% or more, it is often preferable to use a compound that does not contain a highly water-soluble substituent such as a sulfo group, a carboxyl group or a boric acid group.

The silver halide photographic light-sensitive material of the present invention is subjected to selenium sensitization and / or tellurium sensitization. The selenium sensitizer used for chemical sensitization of the silver halide photographic light-sensitive material of the present invention contains a wide variety of selenium compounds. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea,
N, N, N'-triethylselenourea, N, N, N'-
Trimethyl-N'-heptafluoroselenourea, N,
N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-
N'-4-nitrophenylcarbonylselenourea),
Selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.),
Selenocarboxylic acids and selenoesters (for example, 2
-Selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), and selenides (diethylselenide, diethyldiselenide, etc.).
Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenium ketones.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally in the range of 10 ^-8 to 10 ^-4 mol per mol of silver halide. Depending on the properties of the selenium compound to be used, the method of addition may be a method of adding it alone or in a mixed solvent of water or an organic solvent such as methanol or ethanol, or a method of adding it by previously mixing with a gelatin solution. However, a method disclosed in JP-A-4-140739, that is, a method of adding the compound in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent is preferable.

Compounds useful as tellurium sensitizers used in the chemical sensitization of the present invention include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N '). -Dimethyltellurourea, N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutyl) Phenylphosphine telluride), telluroamides (e.g. telluroacetamide, N, N-dimethyltellurobenzamide),
Examples include telluroketones, telluroesters, and isotellurocyanates. The technology for using these tellurium sensitizers is based on the technology for using selenium sensitizers.

In the present invention, chemical sensitization can be carried out with a selenium compound or tellurium compound and a sulfur compound, and further with a noble metal salt such as a gold salt. Further, reduction sensitization can be performed, or sensitization can be performed by combining these methods. Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate, and gold complexes of thioureas, rhodanines, and other various compounds.

The amounts of the sulfur sensitizer and the gold sensitizer used are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but usually 1 × per mole of silver halide. It is preferably from 10 ^-4 mol to 1 × 10 ^-9 mol. More preferably, 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸
Is a mole.

In the present invention, the chemical sensitizer is added
It may be dissolved in water or alcohols or other inorganic or organic solvents and added in the form of a solution. The form of a dispersion obtained by emulsifying and dispersing using a solvent such as a water-insoluble solvent or gelatin. May be added.

In the present invention, sulfur sensitization, selenium sensitization, tellurium sensitization and gold sensitization may be performed simultaneously or separately and stepwise. In the latter case, favorable results may be obtained if selenium sensitization or gold sensitization is performed after moderately or during the sulfur sensitization.

In the present invention, it is also preferable to use reduction sensitization in combination. The reduction sensitization is preferably performed during the growth of silver halide grains. As a method of applying during the growth, not only a method of performing reduction sensitization in a state where silver halide grains are growing, but also a method of performing reduction sensitization in a state where growth of silver halide grains is interrupted, and then performing reduction sensitization. It also includes a method of growing the perceived silver halide grains. Preferred examples of the reduction sensitizer include thiourea dioxide, ascorbic acid, and derivatives thereof. Other preferable reducing agents include polyamines such as hydrazine and diethylenetriamine, dimethylamine borane, and sulfite.

The amount of the reduction sensitizer to be added depends on the type of the compound, the particle size of silver halide grains, the composition and crystal habit, the temperature of the reaction system, p
It is preferable to change the concentration depending on environmental conditions such as H and pAg. For example, in the case of thiourea dioxide, approximately 0.01 to 2 mg per mol of silver halide is used as a rough guide.
Is preferable. In the case of ascorbic acid, the range is preferably about 50 mg to 2 g per mol of silver halide.

The emulsion may be subjected to so-called silver ripening, which is a kind of reduction sensitization technique, by adding a water-soluble silver salt. Silver nitrate is preferred as the water-soluble silver salt, and the pAg at the time of silver ripening is suitably from 1 to 6, preferably from 2 to 4. temperature,
The conditions such as pH and time are preferably in the above-mentioned conditions for reduction sensitization. As a stabilizer of the reduction-sensitized silver halide emulsion, a general stabilizer can be used, and an antioxidant disclosed in JP-A-57-82831 can be used.
V. S. Gahler's paper [Zeithlift
fur wissenschaftliche Ph
autographie Bd. 63, 133 (196
9)] and the use of thiosulfonic acids described in JP-A-54-1019 often gives good results.
These compounds may be added at any stage of the emulsion production process from the crystal growth to the preparation process immediately before coating.

In the chemical ripening step of the silver halide emulsion according to the present invention, when the pH, pAg and temperature of the emulsion are changed before and after the addition of selenium and / or tellurium sensitizer, a remarkable fog suppression effect is obtained. Is recognized.

The silver halide photographic light-sensitive material of the present invention may be spectrally sensitized with a spectral sensitizing dye. Oxonol dyes are included. Particularly useful dyes are those belonging to the cyanine, merocyanine and complex merocyanine dyes.

In addition to these spectral sensitizing dyes, dyes having no spectral sensitization or substances exhibiting supersensitizing effect may be added to the emulsion layer. Silver halide 1
The appropriate amount of the spectral sensitizing dye per mole varies depending on the total surface area of the silver halide grains in the emulsion, but is preferably less than 500 mg. More preferably, the amount is less than 400 mg.

In the present invention, the spectral sensitizing dye is one that adsorbs to silver halide grains and contributes to sensitization. The spectral sensitizing dye used in the present invention can be arbitrarily selected as long as it has a spectral sensitizing function. In addition, in the application to X-ray medical light-sensitive materials utilizing a phosphor emitting green light, the spectral sensitizing dye of the present invention is adsorbed on silver halide emulsion grains, and when the reflection spectrum is measured, the phosphor is used. It is preferable that the J-band is formed in the same wavelength region as the green light from the light source. That is, the maximum absorption wavelength is preferably 520 to
It is preferable to select and combine spectral sensitizing dyes such that a J-band having the maximum absorption in the region of 555 nm is formed. More preferably 530-553 nm
And most preferably 540 to 550 nm.

As a solvent for the sensitizing dye, a conventionally used water-miscible organic solvent can be used. For example, alcohols, ketones, nitriles, alkoxy alcohols and the like have been used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol,
There are 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol and the like. Also, it can be added as an acidic solution.

A surfactant may be used as a dispersant for the spectral sensitizing dye, and any of anionic, cationic, nonionic and amphoteric surfactants can be used as the surfactant. . Further, the spectral sensitizing dye may be added as a dispersion in the form of solid fine particles, rather than in the case where it is added as a solution of an organic solvent.

The spectral sensitizing dye can be added at the time of chemical ripening, particularly preferably at the start of chemical ripening.
By adding the silver halide emulsion according to the present invention from the nucleation step to the end of the desalting step, a highly sensitive silver halide emulsion having excellent spectral sensitization efficiency can be obtained. At any time after the chemical ripening step and immediately before the coating step, the same or another kind of spectral sensitizing dye is added and added to the above-mentioned step (from the nucleation step to the end of the desalting step). You may.

Next, the silver halide grains used in the present invention will be described.

The silver halide grains of the silver halide emulsion used in the present invention include silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Silver grains can be used arbitrarily, and particularly preferred are silver iodobromide, silver chloroiodobromide and silver chloride.

The silver halide grains used in the present invention may be any silver halide grains such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. It can be used, but when the silver iodide content exceeds 1 mol%, the fogging suppressing effect of the present invention is remarkably reduced. Therefore, when silver iodide is contained in silver halide grains, the content is preferably 1% or less.

At this time, the tabular silver halide grains are particularly preferably silver iodobromide, silver chloroiodobromide and silver chloride. The tabular silver halide grains used in the present invention may have a uniform composition, but have a core / shell type structure having at least two layer structures having substantially different halogen compositions in the silver halide grains. The grains are preferably contained in the photosensitive silver halide emulsion layer in an amount of 50% or more and 100% by number.

The core / shell type structure grains may have a halogen composition region different from that of the core at the grain center. In such a case, the halogen composition of the seed grains may be any combination of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride and the like.

The average silver iodide content of the silver halide emulsion according to the present invention is preferably 2 mol% or less, more preferably 0.01 to 1.0 mol%. Of the grains having a layer structure with a different halogen composition, grains having a high silver iodide layer inside the grains and a low silver iodide layer or a silver bromide layer on the outermost layer are preferred. At this time, the silver iodide ratio of the inner layer (core) having the highest silver iodide content is preferably 2.5 mol% or more, more preferably 5 mol% or more. The silver iodide content is 0 to 5 mol%, preferably 0 to 5 mol%.
Preferably, the silver iodide content of the core is at least 3 mol% or more than the silver iodide content of the shell.

The tabular silver halide grains preferably used in the present invention have an average ratio (average aspect ratio) of grain diameter / thickness (aspect ratio) of 2 or more. The average aspect ratio of the tabular silver halide grains used in the present invention is preferably from 2 to 12, more preferably from 3 to 12.
８8.

The outer wall of the crystal of the silver halide grain according to the present invention may be substantially (111) plane or (100) plane.
The 1) plane and the (100) plane may be combined, but especially in the case of rapid processing in which the development time is less than 20 seconds, the two main planes of the silver halide grains have the (100) plane. When the average silver chloride content is 20 mol% or more, the effect of the present invention is remarkably exhibited.

The silver halide grains according to the present invention may be polydisperse or monodisperse, but are preferably monodisperse. Specifically, when the width of the distribution is defined by the relative standard deviation (coefficient of variation) expressed by (standard deviation of particle size / average particle size) × 100 = width (%) of particle size distribution, 2
It is preferably at most 5%, more preferably at most 20%, particularly preferably at most 15%.

The tabular silver halide grains preferably have a small thickness distribution. Specifically, (standard deviation of thickness /
Average thickness) × 100 = When the width of the distribution is defined by the width (%) of the thickness distribution, it is preferably 25% or less,
It is more preferably at most 20%, particularly preferably at most 15%. Further, the distribution of the halogen content of each grain in the tabular silver halide grain emulsion is preferably small. Specifically, (standard deviation of halogen content /
(Average halogen content) × 100 = When the breadth of the distribution is defined by the breadth (%) of the halogen content, it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less. % Or less.

In the present invention, when tabular silver halide grains having twin planes are used, the shape of the main plane is preferably hexagonal. Hexagonal tabular grains (hereinafter also referred to as hexagonal tabular grains) are defined as the main plane (11).
1) The shape of the surface is hexagonal, and the maximum adjacency ratio is 1.
0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. If the maximum adjacent side ratio of the hexagonal tabular grains is 1.0 to 2.0, the corners thereof are preferably rounded. The length of a side having a rounded corner is represented by the distance between the intersection of the extended straight line portion of the side and the extended straight line portion of the adjacent side. It is also preferred that the tabular grains are further rounded and are substantially circular. It is preferable that at least one half of each side forming the hexagon of the hexagonal tabular grain is substantially a straight line. More preferably, the adjacent side ratio is 1.0 to 1.5.

The halogenated grains according to the present invention may have dislocations. The dislocation is described, for example, in J. Mol. F. Hamilto
n, Photo. Sci. Eng, 57 (1967),
T. Shiozawa, J .; Soc. Photo. Sc
i. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a sharper observation can be obtained by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). it can.

Regarding the number of dislocations in silver halide grains,
It is desirable that at least 50% (number) of grains containing one or more dislocations be present, and the higher the ratio (number) of the number of tabular grains having dislocation lines, the better.

The silver halide grains used in the present invention are:
So-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is preferably from 0.2 mol% to 2.0 mol% with respect to the silver amount, and the conversion may be performed during physical ripening or after completion of physical ripening. As a halogen conversion method, usually, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition on the grain surface before the halogen conversion is added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 μm or less.
０．１0.1 μm. The silver halide grains of the present invention are preferably grown by, for example, a method of depositing silver halide on a seed crystal as described in Examples of JP-A-60-138538.

In preparing the emulsion used in the present invention, a known silver halide solvent such as ammonia, thioether, or thiourea may be present during the step of forming seed grains and growing the seed grains. Conditions for enlarging the produced seed grains in order to obtain tabular silver halide grains include, for example, JP-A-51-39027 and JP-A-55-142329.
As described in JP-A Nos. 58-113928, 54-48521 and 58-49938, a water-soluble silver salt solution and a water-soluble halide solution were added by a double jet method, and the addition speed was increased to increase the particle size. Accordingly, a method of gradually changing the temperature within a range in which new nucleation does not occur and Ostwald ripening does not occur may be used. As another condition for enlarging the seed grains, a method of adding silver halide fine grains, dissolving and recrystallizing the grains, as shown in the 88th Annual Meeting of the Photographic Society of Japan, 1988, may be used. For growth, an aqueous silver nitrate solution and an aqueous halide solution can be added by a double jet method, but they can also be supplied into the system as fine silver halide particles. The addition rate is preferably such that no new nuclei are generated, and at a rate at which the size distribution does not spread due to Ostwald ripening, that is, 30 to 100% of the rate at which new nuclei are generated.

The silver halide grains according to the present invention can be produced in the course of forming and / or growing grains by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (complex salt). ) And at least one metal ion selected from iron salts (including complex salts) so that these metal elements can be contained inside the particles and / or in the particle surface layer. By placing in an atmosphere, a reduction sensitizing nucleus can be provided inside the grain and / or on the grain surface. Also, at a desired point in the particle formation, an oxidizing agent such as hydrogen peroxide or thiosulfonic acid can be added.

In the silver halide emulsion of the silver halide photographic light-sensitive material of the present invention, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may remain contained. When the salts are removed, Research Disclosure (hereinafter abbreviated as RD) No. 17643
It can be performed based on the method described in Item II.

In the present invention, the silver halide emulsion layer may contain grains having various shapes as long as the effects of the present invention are not impaired. Latex used in the present invention,
Those which have no or very little adverse effect on the following points even when used in a silver halide photographic element are preferred. That is, the latex surface is photographically inert and has very little interaction with various photographic additives. As an example, dyes and dyes are adsorbed and the photographic element is hardly stained with color. Further, it is difficult to adsorb a development accelerator, a development inhibitor, and the like, which affect the speed of development, and hardly affect sensitivity and fog. In the production of a photographic element, the photographic solution in which the latex of the present invention is dispersed has little pH dependency and is hardly affected by ionic strength, so that coagulation and sedimentation is difficult. It is considered that the fact that the latex that can be used in the present invention has the above-mentioned properties greatly affects the monomer composition and properties of the latex. An index called a glass transition point is often used for latex. The higher the transition point is, the harder it becomes and cannot serve as a buffer. For this reason, considering the photographic characteristics, the selection of the composition and its use amount are not simple. Latexes using monomers such as styrene, butadiene, and vinylidene are well known.

It is said that the introduction of a monomer having a carboxylic acid group such as acrylic acid, itaconic acid or maleic acid during the synthesis of latex reduces the influence on the photographic properties, and such synthesis is often attempted. The latex obtained by such a combination may contain a methacrylate unit to appropriately set the glass transition point according to the light-sensitive material.

In the present invention, the amount of the hydrophilic binder is 1.0 to 3.5 g / m ² per one side. This amount range is advantageous for achieving the effects of the present invention, and when the development time is less than 20 seconds, it is more preferably 1.0 to 3.0 g / m ² per one side.

In the silver halide photographic light-sensitive material of the present invention, a compound represented by the following formula [H] can be used as a hydrazine derivative.

[0077]

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(Wherein E represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents a — (CO) n— group, a sulfonyl group, a sulfoxy group, a —P
(＝ O) represents a R ₃₅ — group or an iminomethylene group; n represents an integer of 1 or 2; E ₁ and E ₂ are each a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl; Represents a group or a substituted or unsubstituted acyl group, and R ₃₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a heterocyclic oxy group, Represents an amino group, a carbamoyl group, or an oxycarbonyl group. R ₃₅ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group and the like. Among the compounds represented by the general formula [H], more preferred are the compounds represented by the following general formula [Ha].

[0079]

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R ₃₆ in the formula is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, thienyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Furthermore, the R ₃₆ preferably contains at least one ballast group or a silver halide adsorption accelerating group.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [Ha], Xa represents a group that can be substituted for a phenyl group, ma represents an integer of 0 to 4, and when ma is 2 or more, Xa may be the same or different. .

In the general formula [Ha], E ₃ and E ₄ have the same meanings as E ₁ and E ₂ in the general formula [H], and both are preferably hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ₃₇ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ₃₇ includes —COOR ₃₈ group and —CON
(R ₃₉ ) (R ₄₀ ) groups (R ₃₈ represents an alkynyl group or a saturated heterocyclic group; R ₃₉ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; R ₄₀ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0088]

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[0089]

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[0090]

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[0091]

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Specific examples of other preferred hydrazine derivatives are described, for example, in US Pat. No. 5,229,248, columns 4 to 60, (1) to (2).
52). The hydrazine derivative according to the present invention can be synthesized by a known method.
No. 229,248, column 59 to column 80, can be synthesized by the method as described.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
^-1 mol, preferably 10 ^-5 to 10 ^-2 mol. The hydrazine derivative preferably used in the present invention is added to a silver halide emulsion layer and / or an adjacent layer thereof.

The hydrazine compound used in the present invention can be used in any layer on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. The optimum amount to be added depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. It is preferably in the range of mol, particularly preferably 10 ^-5 to 10 ^-2 mol. In the present invention, three or more hydrazine compounds can be contained in any layer in any state. In the present invention, it is preferable to use a nucleation accelerator in order to effectively promote high contrast. Examples of the nucleation accelerator include compounds described in Japanese Patent Application No. 6-103982, pp. 28-29.
No. 982 DI, pages 30 to 35 (Na-1) to (Na-
22) or compounds described as (Nb-1) to (Nb-12), but are not limited thereto. Specific examples of other preferable nucleation promoting compounds are exemplified in (2-1) described in JP-A-6-258751.
To (2-20) and the compounds of (3-1) to (3-6) described in JP-A-6-258751. The nucleation accelerator can be used in any layer on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. The amount of the nucleation accelerator used in the light-sensitive material is 5 × 10 ^-7 per mol of silver halide.
モ ル 5 × 10 ^-1 mol, preferably 5 × 10 ^-1 mol
The range is preferably from ^{-6 to} 5 x ^10-2 mol.

When the silver halide photographic material of the present invention is applied to a silver halide photographic material for plate-making printing, the following compounds are contained in the constituent layers of the silver halide photographic material. Is preferred.

(1) Solid dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Tetrazolium compound JP-A-6-208188, page (8) [0059]-
(10) Compound described on page [0067] (7) Pyridinium compound JP-A-7-110556 (5) page [0028]-
(29) Compound described in [0068] (8) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) The compound described on page.

The above-mentioned additives and other known additives can be used in the silver halide photographic light-sensitive material according to the present invention. These are described in (RD) No. 17643
(December 1978), 18716 (November 1979)
Mon.) and 308119 (December 1989). The following table shows the compound types and locations described in these three (RD).

[0098]

[Table 1]

The support used in the silver halide photographic light-sensitive material according to the present invention is preferably a transparent plastic support. As the plastic support, for example, a support made of polyethylene terephthalate, polyethylene naphthalate, triacetate cellulose, a polystyrene compound, or the like is used. Further, a support of a stretched film (SPS) made of a styrene-based polymer having a syndiotactic structure or a composition containing the same may be used.

Next, the development processing of the light-sensitive material of the present invention will be described.

Preferred developers for developing the light-sensitive material of the present invention include dihydroxybenzenes such as hydroquinone and para-aminophenols such as p-aminophenol, N-methyl-p-aminophenol, and 2,4-dichlorobenzene. Examples of 3-pyrazolidones such as amiphenol include 1-phenyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-
It is preferable to use 4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like, and to use them in combination.
The preferred amount of the paraaminophenols and 3-aminopyrazolidones used is 0.004 mol / l, more preferably 0.04 to 0.12 mol / l. In addition, dihydroxybenzenes, para-aminophenols,
The total number of moles of the 3-pyrazolidones is preferably 0.1 mol / liter or less.

Further, when the present invention is applied to a silver halide photographic light-sensitive material for color photography, processing with a generally known processing solution for color may be performed.

As preservatives for the developer, sulfites such as potassium sulfite, sodium sulfite, reductones,
For example, it may contain piperidinohexose reductone and the like, and these are preferably used in an amount of preferably 0.2 to 1 mol / l, more preferably 0.3 to 0.6 mol / l. Also, addition of a large amount of ascorbic acids leads to processing stability. Examples of the alkali agent for the developer include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate. Further, buffers such as saccharose, acetoxime, 5-sulfosalicylic acid, phosphates and carbonates may be used. The content of these chemicals should be adjusted to a pH of the developer of 9.0 to 13, preferably pH 10 to 1.
Choose 2.5.

As a dissolution aid for the processing agent, polyethylene glycols and esters thereof can be contained, and as a sensitizer, for example, a development accelerator such as a quaternary ammonium salt, a surfactant and the like can be contained. Silver sludge inhibitors, sulfides, disulfide compounds, cysteine derivatives or triazine compounds are preferably used as the silver sludge inhibitor in the treating agent.

As the organic inhibitor in the treating agent, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benzotriazole, tetrazole and thiadiazole compounds are used. Sodium bromide as an inorganic inhibitor,
Contains potassium bromide, potassium iodide and the like. In addition,
L. F. A. Menson, "Photographic Processing Chemistry," Focal Press (19
66), pages 226-229, U.S. Pat.
No. 15,2,592,364, JP-A-48-649
No. 33 may be used. As a chelating agent for concealing calcium ions mixed in tap water used for the treatment liquid, JP-A-Hei.
The chelate stabilization constant with iron described in US Pat.
The above chelating agents are preferably used.

As the inorganic chelating agent, there are sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate and the like. As the developing hardener, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used.

The processing temperature of the developer of the present invention is preferably 25 to 50 ° C., more preferably 30 to 40 ° C.

The silver halide photographic light-sensitive material of the present invention can be processed in an automatic processor in a total processing time of 10 to 30 seconds, preferably 10 to 25 seconds. The total processing time in the present invention refers to the total processing time of Dry to Dry.

In the present invention, the replenishment replenishes the treatment agent fatigue and the oxidation fatigue equivalent. The replenishment method is disclosed in JP-A-55-1.
No. 26243, width and feed speed, replenishment by area, described in JP-A-60-104946,
Area replenishment controlled by the number of continuous processing described in No. 9156 may be used.

In the present invention, the replenishing amount of the developer is processed at 15 ml or less per quarter. Preferably 1 to
Treatment with 15 ml.

The fixing solution used in the processing method of the present invention may include a fixing material generally used in the art. Examples of the fixing agent include thiosulfates such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable in view of the fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably in the range of 0.8 to 3 mol / l. The fixing solution of the present invention may perform an acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like. The fixing solution of the present invention may further contain a preservative such as sulfite or bisulfite, a pH buffer such as acetic acid or boric acid, a mineral acid (sulfuric acid, nitric acid) or an organic acid (citric acid, oxalic acid or malic acid). ), A pH adjusting agent such as a metal hydroxide (potassium hydroxide, sodium hydroxide) or a chelating agent having a water softening ability. Examples of the fixing accelerator include thiourea derivatives and thioethers.

[0112]

The present invention will be described below in detail with reference to examples.

Example 1 <Preparation of Em-1> A tabular silver iodobromide grain emulsion was prepared as follows.

[0114] A1 ossein gelatin 24.2g Water _{9657ml HO (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) (10% methanol aqueous solution) 1.20 ml potassium bromide 10.8 g 10% nitric acid 160 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 841 g with water 2825 ml C1 ossein gelatin 121 g water 2040 ml HO (CH ₂ CH ₂ O) _n − _{[CH (CH 3) CH 2} O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) (10% aqueous solution of methanol) 5.70ml D1 1.75N potassium bromide aqueous solution following silver potential control amount Using a mixing stirrer described in JP-B-58-58288 at 35 ° C., add each of solution B1 and solution C1
Nucleation was performed by adding 75.0 ml by the simultaneous mixing method over 2.0 minutes. After stopping the addition of the solution B1 and the solution C1, it takes 60 minutes to raise the temperature of the solution A1 to 60 ° C.
, The total amount of D1 was added, the pH was adjusted to 5.5 with 3% KOH, and then the solution B1 and the solution C1 were added again by the simultaneous mixing method at a flow rate of 55.4 ml / min for 42 minutes. . This temperature rise from 35 ° C. to 60 ° C. and solution B
1. During the re-simultaneous mixing by C1, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to +8 mV and +30 mV, respectively, using the solution D1.

After completion of the addition, the pH was adjusted to 6.0 with 3% KOH, and immediately after that, desalting was performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains has a maximum adjacent side ratio of 1.
It was confirmed by an electron microscope that the particles were composed of 0 to 2.0 hexagonal tabular grains, and that the average thickness of the hexagonal tabular grains was 0.090 μm and the average particle diameter (in terms of circular diameter) was 0.510 μm.
Subsequently, the emulsion was heated to 53 ° C., and after adding predetermined amounts of the following spectral sensitizing dyes A and B as a dispersion of solid fine particles, 4-hydroxy-6-methyl-1,3,3a, 7-
A mixed aqueous solution of tetrazaindene (TAI), adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate, a silver iodide fine grain emulsion and a dispersion of triphenylphosphine selenide were added, and ripening was performed for a total of 2 hours and 30 minutes. did.

At the end of ripening, a further stabilizer (TAI)
Was added in an appropriate amount. Spectral sensitizing dyes and other additives and their amounts (per mole of AgX) are shown below.

Spectral sensitizing dye (A): 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl)
-Anhydrous 450 of oxacarbocyanine-sodium salt
mg, spectral sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di-
(4-sulfobutyl) -benzimidazolocarbocyanine-thorium anhydride 8 mg, (TAI) 60 mg, adenine 15 mg, sodium thiosulfate 5.0 mg, ammonium thiocyanate 50 mg, chloroauric acid 2.5 mg,
5 mmol of silver iodide fine grain emulsion (average particle size: 0.05 μm), 6.0 mg of triphenylphosphine selenide, and 750 mg of stabilizer (TAI).

The dispersion of the solid fine particles of the spectral sensitizing dye was prepared according to the method described in JP-A-5-297496. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used at 3,500 rpm.
m for 30-120 minutes.

A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Next, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above experiment.

<Preparation of Em-2> Em- as a seed emulsion
1 and the following four kinds of solutions described below were used to prepare tabular silver iodobromide grain emulsions Em-2.

[0121] A2 ossein gelatin _{19.04g HO (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) (10 % Methanol aqueous solution) 2.00 ml Potassium iodide 7.00 g Em-1 (seed emulsion) 1.55 mol equivalent Make up to 2800 ml with water.

B2 Potassium bromide 1493 g Make up to 3585 ml with water.

C2 Finish with silver nitrate 2131 g water to 3585 ml.

D2 Fine grain emulsion (*) composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) Equivalent to 0.028 mol * 5.0 weight containing 0.06 mol of potassium iodide 2 liters of an aqueous solution containing 7.06 moles of silver nitrate and 7.06 moles of potassium iodide were added to 6.64 liters of a 10% aqueous gelatin solution over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are formed, the pH is adjusted using an aqueous sodium carbonate solution.
Was stirred vigorously while maintaining the solution A2 at 55 ° C., and half the amount of the solution B2 and the solution C2 were added thereto by a double-jet method over 35 minutes. Was kept at 5.8. 7. Adjust the pH to 8 with a 1% KOH solution.
After adjusting the amount to 8, a part of the solution B2 and a part of the solution C2, and the entire amount of the solution D2 were added by a simultaneous mixing method. After adjusting the pH to 6.0 with 0.5% citric acid, solution B2 and solution C
The remaining amount of No. 2 was added by a double jet method over 25 minutes. During this time, the pAg was kept at 8.9 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate. That is, they were added at an appropriate addition rate so as to prevent generation of small particles other than the growing seed particles and to prevent polydispersion by Ostwald ripening.

After completion of the addition, desalting, washing and redispersion were carried out in the same manner as in Em-1, and after redispersion, the pH was adjusted to 5.8 at 40 ° C.
0 and pAg were adjusted to 8.2. When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.91 μm.
m, average thickness 0.23 μm, average aspect ratio about 4.
0, tabular silver halide grains having a grain size distribution of 20.5%. Subsequently, after the emulsion was heated to 47 ° C,
After adding predetermined amounts of the silver iodide fine grain emulsion and the spectral sensitizing dyes A and B as a solid fine dispersion, a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and triphenylphosphine selenide are added. The dispersion was added and aged for a total of 2 hours and 30 minutes.

At the end of ripening, an appropriate amount of (TAI) was added as a stabilizer. Spectral sensitizing dyes and other additives and their amounts (per mole of AgX) are shown below.

390 mg of spectral sensitizing dye (A), 4 mg of spectral sensitizing dye (B), 10 mg of adenine, 3.3 mg of sodium thiosulfate, 50 mg of ammonium thiocyanate,
2.0 mg of chloroauric acid, silver iodide fine grain emulsion (for 5 mmol of silver), 4.0 mg of triphenylphosphine selenide,
750 mg of stabilizer (TAI) were added.

The silver iodide fine grain emulsion is a fine grain emulsion comprising 3% by weight of gelatin and silver iodide grains (average grain size: 0.05). Further, a solid fine particle dispersion of the spectral sensitizing dye was prepared by a method according to the method described in Japanese Patent Application No. 4-99437.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been adjusted to 27 ° C. in advance, and 3,5,5 was added using a high-speed stirrer (dissolver).
Obtained by stirring at 00 rpm for 30-120 minutes. The dispersion of the selenium sensitizer was prepared as follows.

That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. On the other hand, photographic gelatin 3.8k
g was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above experiment.

Next, the emulsion Em- sensitized as described above was used.
A mixed emulsion containing 60% and 40% of each of No. 1 and Em-2 was prepared, and the following additives were further added to prepare an emulsion coating solution. At the same time, a coating solution for the protective layer was prepared.

Next, a polyethylene terephthalate film base for X-rays colored blue at a concentration of 0.15 (having a thickness of 1
The following coating solution for the emulsion layer and the coating solution for the protective layer are simultaneously coated on both sides of a support having the following transverse light-shielding layers previously coated on both sides of the support at a predetermined coating amount of 75 μm). And dried to prepare evaluation samples 1- (1) to 1- (7).

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AD-2) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² General formula (1) of the present invention Compound represented by-(3) Amount described in Table 2 Compound (I) 5 mg / m ² Latex (L) 0.2 g / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium Salt 5 mg / m ² Colloidal silica (average particle size 0.014 μm) 10 mg / m ² Hardener (A) 2 mg / m ² Second layer (emulsion layer) The following various additives were added to each emulsion obtained above. added.

Compounds of the Present Invention Represented by General Formulas (1) to (3) Amounts shown in Table 2 Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1 5,3,5-Triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sulfone sodium 5 mg / m ² compound (H) _{^{.5mg / m 2 n-C 4}} H 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 350mg / m 2 Colloidal silica 0.5 g / m ² Latex (L) 0.2g / m ² Dextran ( (Average molecular weight: 1000) 0.2 g / m ² Compound (P) 0.2 g / m ² Compound (Q) 0.2 g / m ² , provided that gelatin was adjusted to 0.8 g / m ² .

Third layer (protective layer) Gelatin 0.6 g / m ² matting agent composed of polymethyl methacrylate (area average particle size 7.0 μm) 50 mg / m ² formaldehyde 20 mg / m ² 2,4-dichloro-6 Hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonyl methyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² polyacryl Sodium acid 30 mg / m ² Polysiloxane (SI) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1)
7 mg / m ² Compound (K) 15mg / m ² Compound (O) 50mg / m ² Compound (S-2) 5mg / m 2 C 9 F 19 -O- (CH 2 CH 2 O) 11 H 3mg / m 2 C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ )-(CH ₂ CH ₂ O) ₁₅ H 2 mg / m ² Compound represented by the general formula (1) of the present invention described in Table 2 C ₈ F ₁₇ SO _{2 N (C 3 H 7) -} (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 2mg / m 2 hardener (B) should be noted, the amount with the material is one-sided partial silver coverage Was adjusted to be 1.3 g / m ² as one surface.

[0136]

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[0137]

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[0138]

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<< Production of Fluorescent Intensifying Screen 1 >> Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Combined polyurethane-based thermoplastic elastomer, Demorac TPKL-5-26 25, solid content 40% (Manufactured by Sumitomo Bayer Urethane Co., Ltd.) 20 g Nitrocellulose (digestibility: 11.5%) 2 g To the above, a methyl ethyl ketone solvent was added, and the mixture was dispersed with a propeller type mixer. Prepared. (Binder / Phosphor ratio = 1/2)
2) Separately, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose are added and dispersed and mixed as a coating liquid for forming an undercoat layer with methyl ethyl ketone to obtain a viscosity of 3 to 6 ps.
(25 ° C.) was prepared. A 250 μm-thick polyethylene terephthalate base (support) into which titanium dioxide has been kneaded is placed horizontally on a glass plate, and the coating solution for forming an undercoat layer is uniformly coated on the support using a doctor blade. The temperature was gradually raised to 100 ° C. to dry the coating film to form an undercoat layer on the support. The thickness of the coating film was 15 μm.

The above-mentioned coating solution for forming a phosphor layer was uniformly coated with a doctor blade to a thickness of 240 μm and dried, and then compressed. Compression was performed using a calender roll at a pressure of 800 kgW / cm ² and a temperature of 80 ° C. After this compression, Example 1 of JP-A-6-75097 was used.
A transparent protective film having a thickness of 3 μm was formed by the method described in (1).

As described above, a fluorescent intensifying screen 1 comprising a support, an undercoat layer, a phosphor layer and a transparent protective film was produced.

(Evaluation of Rapid Processability) The obtained sample was sandwiched between fluorescent intensifying screens 1 and irradiated with X-rays through a penetrometer type B (manufactured by Konica Medical Co., Ltd.). Using the SR-DF processing solution, processing was performed at a developing temperature of 35 ° C. for a total processing time of 45 seconds (all were Konica Corporation)
Made). At this time, the replenishment rate of the processing solution was 210 ml / m ^{2 for} both the developing solution and the fixing solution. In the evaluation of the fluorescent intensifying screen 1 at this time, the reciprocal of the X-ray exposure required for the sample A-1 to obtain a density of the minimum density +1.0 in the evaluation of the fluorescent intensifying screen 1 was shown as a relative value with 100.

The fog density difference from the sample A-1 at this time was expressed as a percentage. A value lower than the value of the sample A-1 was evaluated as good, and a value higher than the value of the sample A-1 was evaluated as poor.

As a substitute evaluation of the storage stability,
After standing at 48 ° C. and 48% RH for 4 hours, it was sealed with a moisture-proof bag and
After leaving at 4 ° C. for 4 days, the same exposure treatment was performed, and the sensitivity and fog were evaluated. The results obtained are shown below.

[0145]

[Table 2]

[0146]

[Table 3]

As is clear from the table, it is found that the sample of the present invention can be processed promptly, has little fog even after storage with time, and has little fluctuation in photographic performance.

(Evaluation of ultra-rapid processing) As in the evaluation of rapid processing, each sample was sandwiched between fluorescent intensifying screens 1 and irradiated with X-rays.
The X-503 automatic developing machine was modified so as to have the following processing time, and processing was performed at a developing temperature of 35 ° C. with an SR-DF processing solution.

Developing time: 4 seconds Fixing time: 3.1 seconds Washing time: 2 seconds Between washing and drying (squeeze): 1.6 seconds Drying time: 4.3 seconds Total processing time: 15 seconds Replenishment amount of processing solution Is 125 ml / m for both developer and fixer
Processed in ² . The sensitivity is defined as the reciprocal of the X-ray exposure required for the sample B-1 to obtain a density of minimum density + 1.0 at this time is 1
The relative value was set to 00. Fog was represented in the same manner as in Table 3 above. Table 4 shows the obtained results.

[0150]

[Table 4]

Table 4 shows that according to the present invention, the total processing time is 1
It had excellent performance even in ultra-rapid processing of 5 seconds.

(Evaluation with Solid Replenisher) Tablets for developing replenishment were prepared according to the following procedures (A, B).

Operation (A) 12,500 g of sodium erythorbate as a developing agent is pulverized in a commercially available bandam mill until the average particle diameter becomes 10 μm. To this fine powder were added 2000 g of sodium sulfite, 2700 g of dimazone S, 1250 g of DTPA, 12.5 g of 5-methylbenzotriazole, 4 g of 1-phenyl-5-mercaptotetrazole and N-acetyl-D, L-penicillamine, and mixed in a mill for 30 minutes. After granulating by adding 30 ml of water for about 10 minutes at room temperature in a commercially available stirring granulator, the granulated product is dried in a fluidized bed dryer for 4 minutes.
After drying at 0 ° C. for 2 hours, the water content of the granulated material is almost completely removed. 1670 g of polyethylene glycol 6000 and 1670 g of mannitol were added to the granules thus prepared.
Was uniformly mixed for 10 minutes using a mixer in a room humidified at 25 ° C. and 40% RH or less, and the obtained mixture was mixed with a tableting machine modified from Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. 8.77 g filling amount per tablet
And compression tableting, and 2,500 development replenishing tablets A
A preparation was made.

Operation (B) 4000 g of potassium carbonate, 2100 g of mannitol and 2100 g of polyethylene glycol 6000 were operated (A)
Pulverize and granulate as in The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture thus obtained was charged with 3.2 g of tablet per tablet using the same tableting machine as described above.
The tablet was compressed to 8 g and compression tableting was performed to prepare 2500 tablets B for replenishment for development.

Next, a replenishing tablet for fixing was prepared by the following operations (C, D).

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water added was 500 m
and perform granulation. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. 4 g of sodium N-lauroylalanine is added to the granules thus prepared, and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture was subjected to compression tableting using a tableting machine similar to that described above with a filling amount per tablet of 6.202 g to prepare 2500 fixing supplement refilling tablets A.

Operation (D) Boric acid 1000 g, aluminum sulfate / 18 hydrate 150
0 g, sodium hydrogen acetate (equimolar mixture of glacial acetic acid and sodium acetate, dried 3000 g), tartaric acid 20
0 g is pulverized and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. 4 g of sodium N-lauroylalanine was prepared in this manner.
Was added and mixed for 3 minutes, and the obtained mixture was charged with a tableting machine similar to that described above to a filling amount of 4.562 g per tablet.
And compression tableting, and 1250 fixing replenishing tablets D
A preparation was made.

Developer Starter Glacial acetic acid 2.98 g KBr 4.0 g Add water to make 1 liter.

At the start of the processing of the developing solution (start of running), the developing solution 1 prepared by diluting 140 developing tablets with diluting water was used.
The processing was started by filling the developing tank with a liquid obtained by adding 330 ml of the starter to 6.5 liters as a starting liquid. The pH of the developer to which the starter was added was 10.4.
It was 5.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. For the running, use an automatic developing machine SRX-502 equipped with a solid processing agent charging member and modified so that the processing speed can be processed in 25 seconds. Exposure is performed so that the density after development processing becomes about 1.0. Large angle size (35.6
× 35.6 cm) were continuously processed on 200 sheets, and then the sample irradiated with X-rays was processed in the same manner to evaluate the color tone of the silver image. During the running, the photosensitive material is 0.62m in the developer.
^Two of the above-mentioned A and B agents were added per 2 and 76 ml of water were added. P when each of A and B is dissolved in 38 ml of water
H was 10.70. 0.62 photosensitive material in fixer
per m ^{2 two} C agents, one D agent and 74 m water
1 was added. The rate of addition of water to each processing agent was started almost simultaneously with the addition of the processing agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the processing agent.

[0161] The sensitivity was shown as a relative value with the reciprocal of the X-ray exposure required for the sample C-1 to obtain a density of minimum density +1.0 at this time, as 100. In the fog, the difference between the sample and the value of C-1 was expressed as a percentage, and a value lower than the value of sample C-1 was indicated as good, and a value higher than that of sample C-1 was indicated as poor. Table 4 shows the obtained results.

[0162]

[Table 5]

Table 5 shows that the sample of the present invention shows the same performance as the comparative sample even when the treatment with the solid processing agent is performed.

Example 2 <Preparation of Em-3> High silver chloride tabular seed emulsion <Solution A> Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Make up to 7,500 ml with water.

<Solution B> Silver nitrate 1500 g Make up to 2500 ml with water.

<Solution C> KI 4 g NaCl 140 g Make up to 684 ml with water.

<Solution D> 375 g of NaCl Make up to 1816 ml with water.

At 40 ° C., JP-B-58-58288
No. 684 ml of solution B in solution A in the mixing stirrer
And the total amount of solution C was added over 1 minute. 14 EAg
After adjusting to 9 mV and aging by Ostwald ripening for 20 minutes, the entire remaining amount of the solution A and the entire amount of the solution D were added over 40 minutes. Meanwhile, EAg was controlled at 149 mV.

Immediately after the addition was completed, desalting and washing were performed to obtain a seed emulsion EM-3. Seed emulsion Em-3 thus prepared
Means that at least 60% of the total projected area of silver halide grains is (1
00) a tabular grain having a plane as a main plane, an average thickness of 0.07 μm, an average diameter of 0.5 μm, and a variation coefficient of 25.
% By electron microscope observation.

<Preparation of Em-4> High silver chloride emulsion A tabular high silver chloride emulsion was prepared using the following four kinds of solutions.

[0171] <solution A> ossein gelatin _{29.4g HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~ 7) 1.25 ml of 10% methanol aqueous solution Equivalent to 0.98 mol of seed emulsion EM-3 Make up to 3000 ml with water.

<Solution B> 3.50 N AgNO ₃ aqueous solution 2240 ml <Solution C> NaCl 455 g Make up to 2240 ml with water.

<Solution D> 1.75 N NaCl aqueous solution The following silver potential control amount At 40 ° C., the entire amount of Solution B and Solution C was simultaneously mixed with Solution A using a mixing stirrer described in JP-B-58-58288. By the method (double jet method), addition growth was performed for 110 minutes so that the flow rate at the end of the addition became three times the flow rate at the start of the addition. During this time, the silver potential is
Was controlled so as to be +120 mV. After completion of the addition, excess salts were desalted and removed by washing with water. After desalting, pH
Adjust to 6.0 and finish to 450 cc / AgX1 mol.

When about 3,000 of the obtained emulsions Em-4 were observed and measured by an electron microscope and analyzed for shape, 80% or more of the total projected area had the (100) plane as the main plane.
The tabular grains had an average diameter of 1.17 μm and an average thickness of 0.12 μm, and the coefficient of variation was 24%.

Subsequently, this high silver chloride emulsion Em-4 was added to 5
After the temperature was raised to 5 ° C., predetermined amounts of silver iodide fine particles shown below and the following spectral sensitizing dyes (1) and (2) were added as a dispersion in the form of solid fine particles. Thereafter, 20 mg of a compound represented by the general formula (1) of the present invention or a comparative compound shown in Table 5 was added per 1 mol of silver halide. Thereafter, a sulfur sensitizer (Sa), a selenium sensitizer (dimethylselenourea (added in the same manner as the selenium sensitizer of Example 1)) and a gold sensitizer (Sb) were further added, for a total of 90 minutes. After completion of ripening, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) as a stabilizer at the end of ripening
Was added in an appropriate amount. Thereafter, the same additives as those of the emulsion coating solution of Example 1 were added to obtain an emulsion coating solution except for the inhibitor of the present invention or a comparative inhibitor, and a sample No. 1 was prepared together with the same transverse light blocking layer and protective layer as in Example 1. 2-1 to 2-8 were produced.

[0176]

Embedded image

Compounds added in ripening step and their amounts (per mole of AgX) Silver iodide fine grain emulsion 5 mmol equivalent Spectral sensitizing dye (A) 300 mg Spectral sensitizing dye (B) 30 mg Sulfur sensitizer (Sa) 0mg Gold sensitizer (Sb) 1.0mg Stabilizer (TAI) 50mg

[0178]

[Table 6]

[0179]

Embedded image

The obtained film sample was sandwiched between fluorescent intensifying screens (1), and the same evaluation as in the ultra-rapid processing in Example 1 was performed. The results are shown in Table 7. Table 8 shows the results of the same evaluation as the evaluation by the solid processing agent of Example 1.

[0181]

[Table 7]

[0182]

[Table 8]

As is clear from Tables 7 and 8, the samples of the present invention have less fogging when stored over time and have less fluctuation in photographic performance. Further, it can be seen that the sample of the present invention can obtain excellent photographic performance even in a processing method by ultra-rapid processing or solid processing agent replenishment.

Example 3 <Em-5> Preparation of tabular silver halide emulsion containing 45 mol% of AgBr and 55 mol% of AgCl In the method of preparing Em-3, 473 g of potassium bromide was added to solution C. The tabular grains Em-5 were prepared in exactly the same manner except that the silver potential during the addition of the solution B and the solution C was controlled to +100 mV. About 3,000 of the obtained emulsions Em-5 were observed and measured with an electron microscope, and the shape was analyzed. As a result, 80% or more of the total projected area had a (100) plane as a main plane, an average diameter of 1.17 μm, and an average of 1.17 μm. The particles were tabular grains having a thickness of 0.12 μm, and the coefficient of variation was 24%.

<Em-6> AgBr: 45 mol%, Ag
Preparation of Tabular Silver Halide Emulsion of Cl: 55 mol% According to the preparation method of Em-5, the addition time of Solution B and Solution C was 9
Except for 0 minute, tabular grains Em-6 were prepared in exactly the same manner.
Approximately 3,000 of the obtained emulsions Em-5 were observed and measured with an electron microscope, and the shape was analyzed.
0% or more has a (100) plane as a main plane and an average diameter of 0.1%.
98 μm, tabular grains having an average thickness of 0.16 μm,
The coefficient of variation was 21%.

The obtained film sample was sandwiched between fluorescent intensifying screens (1) and subjected to the same evaluation of storability over time and rapid processing as in Example 1 and evaluation with a solid replenisher. It had stable photographic characteristics with less fogging.

Example 4 Preparation of photosensitive material for printing plate making (for bright room) Monodispersity 8.8%, average particle diameter 0.13 μm, silver chloride content 98 mol%, silver bromide content 2 mol%, An emulsion containing (NH ₄ ) ₂ OsCl ₆ at 5 × 10 ⁻⁵ mol per mol of silver was used inside the grains.

On the front side of the support provided with an antistatic layer and an antihalation layer on the back side, a high-speed emulsion layer, a low-speed emulsion layer,
The lower layer of the emulsion protective layer and the upper layer of the emulsion protective layer were sequentially coated. As a method for sensitizing the high-sensitivity emulsion layer, hypo 8 per mole of silver was used.
2 mg, KSCN 2 mg, chloroauric acid 15.4 mg, diphenylpentafluorophenyl selenide 5 mg and temperature 7
An emulsion sensitized with gold, sulfur and selenium at 0 ° C. for 48 minutes was used.

The sensitization of the low-sensitivity emulsion layer was carried out by using a volume average particle size of 0.1.
08 μm particles, similarly at 55 ° C., 44 minutes gold,
Used with sulfur and selenium sensitization. The difference in sensitivity between the high-speed emulsion and the low-speed emulsion was 26%.

The amount of gelatin in the emulsion layer was 1 g / m ^{2 for} the high-sensitivity and low-sensitivity emulsion layers, respectively, and the copolymer latex [polymethyl methacrylate ₃₀ , ethyl acrylate ₄₀ , butyl acrylate ₂₈ , acrylic acid ₂ ] (subscripts 0.5 g / m ² , and the amount of silver added was 1.5 g / m ^{2 for} both the high-speed emulsion layer and the low-speed emulsion layer.
It was m ^2. The upper layer and the lower layer of the emulsion layer each contained 4 × 1 hydrazine compound (Example H-13) per mole of silver.
0 ^-3 mol, and the low-sensitivity emulsion layer amine compound (N-
3) was added in an amount of 1 × 10 ⁻³ mol per mol of silver, and 2 × 10 ⁻³ mol of the compound (R) was added. Further, in the upper and lower layers of the emulsion layer, 0.02 g of sodium nonylphenoxydocosaethylene oxide sulfonate, 0.002 g of benzotriazole, and 1-butanesulfonic acid-2,3 per square meter were used.
-0.001 g of dithiacyclohexane, 0.003 g of adenine, 0.06 g of polystyrenesulfonic acid having a molecular weight of 680,000, and 0.04 g of styrene-maleic acid copolymer
g, 0.05 g of polyvinylpyrrolidone and the compound of the general formula (1) of the present invention or a comparative compound were added as shown in Table 9.

[0191] Emulsion protective layer upper and lower gelatin with amounts respectively ^{0.4g / m 2, 0.5g / m} 2, the amount per latex both layers 0.2 g / m ^2, an average particle diameter of 3.3μ
0.03 g of a silicon dioxide matting agent on the protective layer
/ M ² . The upper layer and the lower layer of the protective layer had an average particle diameter of 0.06 μm having a monodispersity of 12% described below.
m of the fine particle dye (AD-3) is 1.3 × 10 3 per m ^2.
-3 mol was added.

The hardening of the hydrophilic colloid layer was performed by adding mucochloric acid at 0.24 mmol per 1 g of gelatin.

[0193]

Embedded image

The sample No. 4- (1) to 4-
As for (4), the storage stability of the sample was evaluated at 23 ° C.
After leaving at 48% RH for 4 hours, the container is sealed in a moisture-proof bag and left at 55 ° C. for 4 days, exposed using a light room printer using an optical wedge for sensitometry, and developed and fixed using an automatic developing machine. , Washing with water and drying. Develop at 35 ° C, 10
Second, fixing was performed at 28 ° C. for 10 seconds, washing was performed at 25 ° C. for 10 seconds, and drying was performed at 60 ° C. for 10 seconds. The compositions of the developer and fixer used are shown below.

Developer composition (per liter of working solution) 1-phenyl-3-pyrazolidone 1.5 g hydroquinone 30 g erythorbic acid 25 g 5-nitroindazole 0.250 g 5-methylbenzotriazole 0.06 g potassium bromide 3.4 g sulfurous acid Sodium 50 g Potassium hydroxide 30 g Boric acid 12 g Water was added to make 1 liter, and the pH was adjusted to 10.20.

Fixer composition (per liter of working solution) Ammonium thiosulfate (72.5% W / V) aqueous solution 240 ml Sodium sulfite 17 g sodium acetate trihydrate 6.5 g boric acid 6.0 g sodium citrate 2 Water salt 2.0 g Acetic acid (90% W / V aqueous solution) 13.6 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ equivalent content: 8.1% W / V aqueous solution) 26.5 g water was added to make up to 1 liter, and the pH was adjusted to 5.6.

(Evaluation of sensitivity and gamma) The obtained developed samples were measured with a PDA-65 (Konica Digital Densitometer). The sensitivities in the table indicate sample No. 4- (1) The relative sensitivity was defined assuming that the sensitivity at a density of 2.5 was 100. Gamma is represented by the tangent of density 0.1 and 3.0,
If the gamma value in the table is less than 7, it cannot be used, and if it is 7 or more and less than 10, it is still insufficient. Only when the gamma value is 10 or more, a very high contrast image is obtained, indicating that the material is a sufficiently practicable photosensitive material. The results are shown in Table 9 below.

[0198]

[Table 9]

As is clear from Table 9, the sample of the present invention has low fog even after storage, and shows little change in photographic performance.

Example 5 <Preparation of Em-7> A silver chloride content of 7 was obtained by using a double jet method.
0 mol%, balance: silver bromide, average particle size 0.09 μm
Of silver chlorobromide core particles were prepared. K ₃ when mixing core particles
7 × 10 ⁻⁸ mol of Rh (NO) ₄ (H ₂ O) ₂ per mol of silver per mol of silver, K ₃ OsC
l ₆ to 40 ° C. in the presence of 8 × 10 ^-6 mol per mol, pH 3.
An aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed while maintaining the silver potential (EAg) at 165 mV. The core particles were shelled using a double jet method with EAg reduced to 125 mV with saline. At this time, K ₂ IrCl ₆ was added to the halide solution.
3 × 10 ⁻⁷ mol per mol of silver, 9 × K ₃ RhCl ₆
10 ^-8 mol was added. Further, KI conversion was performed using silver iodide fine grains, and the resulting emulsion had an average grain size of 0.15.
μm core / shell monodisperse (coefficient of variation: 10%) silver chloroiodobromide (silver chloride content: 70 mol%, silver iodobromide content: 0.1%).
2 mol%, the balance being silver bromide).

Next, a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, as described in JP-A-2-280139).
No. 287 (3), Exemplified compound G-8). The EAg after desalting was 190 mV at 50 ° C.

The resulting emulsion was mixed with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene at 1.5 × 10 ^-3 mol per mol of silver and potassium bromide at 8.5 ×. 1
^0-4 moles and citric acid were added. Then the pH was set to 5.
6. After adjusting the EAg to 123 mV, 1 × 10 ⁻³ mol of sodium p-toluenesulfonylchloramide trichloride (chloramine T) was added to react, and then the inorganic sulfur S8 compound dispersed in the solid ( Seishin Enterprise Co., Ltd.
; PM-1200, saponin were added, and the average particle size was 0.5
2 × 10 ^-5 mol).

[0203] Then, as shown 1.5 × 10 ^-5 mol aurate chloride, formula according to dimethylselenourea to 1.5 × 10 ^-5 mol and the present invention the compound or comparative compound (1) in Table 10 And subjected to chemical ripening at a temperature of 55 ° C. until the maximum sensitivity was obtained.

Next, at 50 ° C., the following sensitizing dye d-1 was added in an amount of 100 mg / mol of silver and trihexylamine in an amount of 5 m / mol.
g, and after further lowering the temperature to 40 ° C, 4-hydroxy-
6 × methyl-1,3,3a, 7-tetrazaindene was used in an amount of 2 × 10 ^-3 mol, 1 × phenyl-5-mercaptotetrazole was used in an amount of 3 × 10 ^-4 mol, and potassium iodide was used in an amount of 5 × 10 ^-4 mol per mol of silver. After the molar addition, the pH was adjusted to 5.1 with citric acid.

<Preparation of Em-8> Silver halide emulsion Em
-7, the reaction temperature was raised to 50 ° C. to reduce the particle size to 0.19.
μm, and the silver halide emulsion A2 was prepared in exactly the same manner except that K ₃ RhCl ₆ in the shell portion was changed to 6 × 10 ⁻⁸ mol. With the same chemical sensitization, the Em-8 emulsion is 40% faster than the Em-7 emulsion.

(Preparation of photosensitive material for printing plate making scanner)
On a support, a gelatin subbing layer having the following formulation 1 so that the amount of gelatin is 0.45 g / m ^2, amount of silver 1.5 g / m ² of silver halide emulsion layers 1 formulation 2 thereon, as the amount of gelatin is 0.65 g / m ^2, further amount of silver 1.5 g / m ² of silver halide emulsion layers 2 of Formula 3 thereon, so that the amount of gelatin is 0.65 g / m ² Further, a coating solution for a protective layer having the following formula 4 was simultaneously and multi-layer coated so that the amount of gelatin became 1.3 g / m ² . On the other side of the undercoating layer, a backing layer of the following formulation 5 was provided with a gelatin amount of 1.5 g / m ^2, and a backing protective layer of the following formulation 6 was provided thereon with a gelatin amount of 0.8 g / m 2. ^The emulsion layer side and the emulsion layer side were simultaneously multilayer-coated at a speed of 200 m / min by a curtain coating method so as to obtain a layer 2 and then cooled and set. Then, the backing layer side was simultaneously multilayer-coated and cooled and set at -1 ° C. A sample was obtained by simultaneously drying both sides.

Formulation 1 (Gelatin undercoat layer composition) Gelatin 4.5 g / m ² Saponin 56.5 mg / m ² Solid disperse dye AD-12 10 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500000) 15 mg / m ² Sterilization Agent (Z) 0.5 mg / m ² Prescription 2 (composition of silver halide emulsion layer 1) Silver halide emulsion Em-7 Amount of silver equivalent to 1.5 g / m ² Sensitizing dye d-1 200 mg / Ag 1 mol hydrazine Compound (H-13) 4 × 10 ⁻³ mol / Ag 1 mol Amino compound N-3 7 mg / m ² Compound (R) 8 × 10 ⁻³ mol /
Ag 1 mol Compound (S-1) 100 mg / m ² Compound of the present invention or comparative compound (described in Table 11) Sodium-di- (3-ethyl-n-butyl) sulfosuccinate 100 mg / m ² 2-pyridinol 1 mg / m ² latex (L1) (particle size 0.25 μm) 0.25 g / m ² hardener h1 2.5 mg / m ² hardener (B) 2.5 mg / m ² sodium-iso-amyl-n-decyl Sulfosuccinate 0.7 mg / m ² Sodium naphthalene sulfonate 8 mg / m ² Saponin 20 mg / m ² Hydroquinone 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyridine 1 mg / m ² Colloidal silica ( (Average particle size: 0.05 μm) 150 mg / m ² ascorbic acid 20 mg / m ² EDTA 25 mg / m ² polystyrene sulfone The pH of the sodium acid 15 mg / m ² coating solution was 5.2.

Formulation 3 (Composition of Silver Halide Emulsion Layer 2) Silver Halide Emulsion Em-8 Amount of silver equivalent to 1.5 g / m ² Equivalent to sensitizing dye d-2 300 mg / Ag 1 mole Hydrazine compound (H-4) 8 × 10 ⁻³ mol / Ag1 mol Amino compound (N-7) 7 mg / m ² Compound (R) 8 × 10 ⁻³ mol / Ag1 mol Sodium-iso-amyl-n-decylsulfosuccinate 1.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² Nicotinamide 1 mg / m ² Gallic acid n-propyl ester 50 mg / m ² Mercaptopyrimidine 1 mg / m ² EDTA 50 mg / m ² Styrene-maleic acid copolymer (molecular weight 7 ten thousand) 10 mg / m ² latex L2 (JP-A 5-66512 Patent example 3 type Lx-3 composition (9)) 0.25g / m ² colloidal silica ( Hitoshitsubu径0.05μm) 150mg / m ² gelatin coating solution pH using phthalated gelatin 4.8
Met.

Formulation 4 (Emulsion protective layer composition) Gelatin 1.3 g / m ² Amino compound N-3 14 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 2 mg / m ² Matting agent: average particle size 3 2.5 μm spherical polymethyl methacrylate 25 mg / m ² Average particle size 8 μm irregular silica 12.5 mg / m ² Compound (S-3) 26.5 mg / m ² Compound (S-1) 50 mg / m ² Slip agent (silicone) Oil) 4 mg / m ² redox compound (C) 25 mg / m ² Polymer latex L3 (particle diameter 0.10 μm) 25 g / m ² colloidal silica (average particle diameter 0.05 μm) 150 mg / m ² Dye f1 20 mg / m ² 1 , 3-vinylsulfonyl-2-propanol 40 mg / m ² hardener (h1) 15 mg / m ² hardener (B) 15 mg / m ² polystyrene sulfonate Sodium phonate 10 mg / m ² Disinfectant (Z) 0.5 mg / m ² (Method of dispersing redox compound) Redox compound (C) 2 g Ethyl acetate 80 g The redox compound is dissolved in the above formulation and mixed with the following gelatin solution.

6 g of 10% TK-AX (manufactured by Takemoto Yushi Co., Ltd.) 180 g of 15% aqueous gelatin 180 g The mixture was preliminarily dispersed at 40 ° C. with a homogenizer for 5 minutes. Remove the ethyl. Make up to 280g with water.

Formulation 5 (composition of backing layer) Gelatin 0.6 g / m ² sodium-iso-amyl-n-decylsulfosuccinate 5 mg / m ² Polymer latex L3 0.3 g / m ² colloidal silica (average particle size: 0. 05μm) 100mg / m ² of sodium polystyrenesulfonate 10 mg / m ² dye f1 65 mg / m ² dye f2 15 mg / m ² dye f3 100mg / m ² 1- phenyl-5-mercaptotetrazole 10 mg / m ² hardener (h- 2) 50 mg / m ² Hardener (B) 50 mg / m ² Zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² Formulation 6 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: average particle size 5 μm Monodisperse polymethyl methacrylate 50mg / m
² Average particle size 3 μm Variable silica 12.5 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Compound (S-3) 1 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / M ² dye f3 100 mg / m ² dye AD-13 (solid dispersion) 20 mg / m ² Compound (S-1) 50 mg / m ² Hardener (h1) 10 mg / m ² Hardener (h2) 10 mg / m ² Sodium polystyrene sulfonate 10mg / m ²

[0212]

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[0213]

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[0214]

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[0215]

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Table 10 shows the details of the obtained samples.

[0219]

[Table 10]

At 23 ° C., 4
After leaving at 8% RH for 4 hours, seal in a moisture-proof bag and
Left for days. Next, step exposure was performed with a laser sensitometer using a 633 nm HeNe laser at 1.5 × 10 ⁻⁷ seconds while changing the amount of light, and an automatic developing machine GR-27 (manufactured by Konica Corporation) was used under the above development conditions. Processing was performed. The obtained developed sample was measured with a PDA-65 (Konica Digital Densitometer). The sensitivities in the table indicate sample No. The relative sensitivity when the sensitivity of 5- (1) at a density of 2.5 was set to 100 was determined.

The development was performed at 25 ° C. for 15 seconds, and the drying was performed at 50 ° C. for 20 seconds. The composition of the developer used is as follows.

(Composition of developer) Per liter of working solution diethyltriaminepentaacetic acid / pentasodium salt 1 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g hydroquinone 20 g 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone 0.85 g potassium bromide 4 g 5-methylbenzotriazole 0.2 g boric acid 8 g diethylene glycol 40 g 8-mercaptoadenine 0.3 g The pH of the used solution becomes 10.4 with KOH (fixing solution composition) Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) 25 ml Used with sulfuric acid The solution pH was adjusted to 4.9.

(Evaluation of sensitivity, gamma) 5- (1) was expressed as a relative sensitivity when the sensitivity at a density of 2.5 was taken as 100. The results obtained are shown in the table below.

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[Table 11]

From the table, it can be seen that the sample of the present invention has excellent preservability, little increase in fog, and no deterioration in sensitivity and gamma.

Example 6 (Preparation of a multilayer color photographic light-sensitive material) In all of the following examples, the amount added in a silver halide photographic light-sensitive material indicates the weight (g) per 1 m ² unless otherwise specified. . Further, silver halide and colloidal silver are shown in terms of silver.

On a triacetylcellulose film support, layers having the following compositions were successively formed from the support side to prepare multilayer color photographic element samples 6-1 to 6-4.

Sample 6-1 (Comparative) First layer: Antihalation layer (HC-1) Black colloidal silver 0.20 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.05 Colored Coupler (CM-2) 0.05 High boiling solvent (Oil-1) 0.20 Gelatin 1.5 Second layer: Intermediate layer (IL-1) UV absorber (UV-1) 0.01 High boiling solvent ( Oil-1) 0.01 gelatin 1.5 Third layer: low-sensitivity red-sensitive emulsion layer (RL) silver iodobromide emulsion silver bromide emulsion (Em-1) 0.8 silver iodobromide emulsion (Em-2) 0.8) Sensitizing dye (S-1) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 2.5 × 10 ^-4 (mol / silver 1 mol) dye (S-3) 0.5 × 10 -4 ( mol / mole of silver) cyan coupler (C-1) 0.5 cyan coupler (C- ) 0.05 Cyan coupler (C-4) 0.5 Colored cyan coupler (CC-1) 0.05 DIR compound (D-1) 0.002 High boiling solvent (Oil-1) 0.5 Gelatin 1.5 Fourth layer: high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 2.0 sensitizing dye (S-1) 2.0 × 10 ^-4 (mol / silver 1 mol) Dye (S-2) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-2) 0 .015 Cyan coupler (C-3) 0.10 Cyan coupler (C-4) 0.25 Colored cyan coupler (CC-1) 0.015 DIR compound (D-2) 0.05 High boiling solvent (Oil-1) 0.2) Gelatin 1.5 Fifth layer: Intermediate layer (IL-2) Gelatin 0.5 Sixth layer: Low Domidori sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 1.0 Sensitizing dye (S-4) 5.0 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-5 1.0 × 10 ⁻⁴ (mol / silver 1 mol) Magenta coupler (M-1) 0.5 Colored magenta coupler (CM-1) 0.01 DIR compound (D-3) 0.02 DIR compound (D -4) 0.02 High boiling point solvent (Oil-2) 0.3 Gelatin 1.0 Seventh layer: Intermediate layer (IL-3) Gelatin 0.8 Eighth layer: High sensitivity green-sensitive emulsion layer (GH) Silver bromide emulsion (Em-3) 1.3 Sensitizing dye (S-6) 1.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) 2.5 × 10 ^-4 ( mole / mole of silver) sensitizing dye (S-8) 0.5 × 10 -4 ( mol / mole of silver) magenta coupler (M-2) 0.05 magenta coupler (M- 0.15 colored magenta coupler (CM-2) 0.05 DIR compound (D-3) 0.01 high boiling solvent (Oil-3) 0.5 gelatin 1.0 9th layer: yellow filter layer (YC) Yellow colloidal silver 0.1 Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Oil-3) 0.1 Gelatin 0.8 Tenth layer: low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide Emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-10) 7.0 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) ) 0.5 Yellow coupler (Y-2) 0.1 DIR compound (D-2) 0.01 High boiling solvent (Oil-3) 0.3 Gelatin 1.0 Eleventh layer: Highly sensitive blue-sensitive emulsion layer ( BH) Silver iodobromide emulsion (Em-4) 0.50 Silver iodobromide emulsion (Em-1) 0.20 Sensitizing dye (S-9) 1.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-10) 3.0 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.30 Yellow coupler (Y-2) 0.05 High boiling solvent (Oil-3) 0.15 Gelatin 1.1 Twelfth layer: First protective layer (PRO-1) Fine particle iodobromide Silver emulsion (average particle size 0.08 μm, AgI 2 mol%) 0.4 UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.05 High boiling solvent (Oil-1) 0. Reference Signs List 1 High boiling point solvent (Oil-4) 0.1 Formalin scavenger (HS-1) 0.5 Formalin scavenger (HS-2) 0.2 Gelatin 1.0 13th layer: Second protective layer (PRO-2) Interface Activator (Su-1) 0.005 Alkali-soluble matting agent (average particle size 2 μm) 0.05 Polymethyl methacrylate (average particle size 3 μm) 0.05 Cyan dye (AIC-1) 0.005 Magenta dye (AIM-1) 0.01 Sliding agent (WAX-1) 0.04 Gelatin 0. 6 In addition to the above composition, each layer contains a coating aid Su-2, a dispersion aid Su-3, a hardener H-1 (40 mg / g gelatin), a stabilizer Stab-1, and an antifoggant AF- 1 was added.

Em-1 Average grain size of 0.46 μm, average silver iodide content of 7.0%, monodisperse surface-low silver iodide-containing emulsion Em-2 Average grain size of 0.30 μm, average silver iodide Emulsion Em-3 having a 2.0% content, monodisperse and uniform composition Em-3, an average grain size of 0.81 [mu] m, an average silver iodide content of 7.0%, and a monodisperse surface-low silver iodide-containing emulsion Em- 4 Emulsion having an average grain size of 0.95 μm, an average silver iodide content of 8.0%, and a monodisperse surface-low silver iodide-containing emulsion

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The samples 6-1 to 6 thus prepared
After performing wedge exposure on each of No.-4 using white light, the following development processing was performed.

Processing step A (38 ° C.) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fix 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Drying The composition of the processing solution used in each processing step is as follows.

[Color developing solution] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2 0.0 g anhydrous potassium carbonate 37.5 g sodium bromide 1.3 g nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g potassium hydroxide 1.0 g Water was added to make 1 liter.

[Bleaching Solution] Ferric ammonium salt of ethylenediaminetetraacetic acid 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water was added to make 1 liter, and the pH was adjusted using aqueous ammonia. = 6.0.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium meta sulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 using acetic acid.

[Stabilizing liquid] Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

(Effect of Fog) The photosensitive material was forcibly stored at 55 ° C. and 80% relative humidity for 3 days in order to evaluate the storage stability of the photosensitive material over time. The decrease was evaluated by ΔSB. The smaller the value, the smaller the decrease in sensitivity during storage and the better. In addition, the fog is represented by a percentage difference from the fog of the sample 6-1. The smaller the value, the smaller the fog occurrence and the better.

The results obtained are shown in Table 12 below. The samples of the present invention exhibited excellent storage stability over time even when applied to color photographic materials.

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[Table 12]

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As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material which can be processed rapidly and has excellent storage stability with time and a processing method thereof can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location G03C 1/09 G03C 1/09 5/26 5/26 5/29 5/29 5/31 5 / 31

Claims (11)

[Claims] 1. A silver halide photographic material having a hydrophilic colloid layer including at least one silver halide emulsion layer on a support, wherein the hydrophilic colloid layer is a mercapto group or a group in which a mercapto group is blocked. 5-6 having at least one water-soluble group
A silver halide photographic material comprising a nitrogen-containing heterocyclic compound. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the nitrogen-containing heterocyclic compound is a compound represented by the following general formula (1). Embedded image (In the formula, Het represents a substituted or unsubstituted 5- or 6-membered nitrogen-containing heterocyclic ring having no mercapto group or a group in which a mercapto group is blocked as a substituent, J represents an a + 1-valent linking group, Q represents a water-soluble group, n represents an integer of 0 to 5, and m and a represent an integer of 1 or more. 3. The silver halide photographic material according to claim 2, wherein the nitrogen-containing heterocyclic compound is a compound represented by the following general formula (2) or (3). Embedded image (In the formula of the general formula (2), W represents an oxygen atom, a sulfur atom, a nitrogen atom, or —C (R ₁ ) (R ₂ ) —, and X represents a nitrogen atom or —C (R ₁ ) —. It represents .Z is .R ₁ representing a mercapto group, or blocked atomic group necessary for forming a nitrogen-containing aromatic heterocyclic 5-6 membered substituted or unsubstituted no mercapto group as a substituent And R ₂ represent a hydrogen atom or a substituent other than a mercapto group or a group in which a mercapto group is blocked, and J, Q, n, and m have the same meanings as in the general formula (1). Where P,
V, Y and T each represent a hydrogen atom, a nitrogen atom, or -C
(R ₁ ) (R ₂ )-. R ₁ , R ₂ , J, Q, n and m have the same meanings as in the general formula (1). ) 4. The silver halide photographic material according to claim 1, wherein two parallel main planes of the silver halide grains have a (100) plane, and an average silver chloride content. Is a tabular silver halide grain having a content of at least 20 mol%. 5. A silver halide photographic light-sensitive material according to claim 1, which is chemically sensitized with a selenium and / or tellurium compound. . 6. The amount of the hydrophilic binder on the support is 1.0.
g to 3.5 g / m ² .
6. The silver halide photographic light-sensitive material according to any one of 5. 7. The silver halide photographic light-sensitive material according to claim 1, wherein said hydrophilic colloid layer contains a hydrazine compound. 8. The silver halide photographic light-sensitive material according to claim 7, wherein the hydrazine compound has a sulfonamide bond. 9. A method for processing a silver halide photographic light-sensitive material, comprising processing the silver halide photographic light-sensitive material according to claim 1. 10. The developer replenishing amount is set at 1 per 1 sheet.
10. The method for processing a silver halide photographic light-sensitive material according to claim 9, wherein the processing is carried out by an automatic processor of 5 ml or less. 11. The method for processing a silver halide photographic light-sensitive material according to claim 9, wherein the processing is performed by an automatic developing machine having a total processing time of 10 to 30 seconds.