JP2001159800A - Method for preparing silver halide photographic emulsion and silver halide photographic sensitive material containing the emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity and less liable to fog even in rapid processing, having improved pressure resistance and less liable to the deterioration of performance in storage. SOLUTION: Chemical sensitization is carried out in the presence of at least one of compounds of formulae 1-14 to prepare the objective silver halide emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

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BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide photographic emulsion and a silver halide photographic light-sensitive material containing the emulsion. The present invention relates to a silver halide photographic light-sensitive material which is improved and has less deterioration in performance upon storage.

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2. Description of the Related Art In recent years, with the progress of electronics, the shortening of access time to video has been dramatically advanced.
Silver halide photographic light-sensitive materials are no exception, and more rapid processing suitability is required. To meet this demand, the sensitivity of silver halide photographic emulsions such as chalcogen sensitization and reduction sensitization using selenium or tellurium compounds has been improved.
Various techniques for rapid processing have been studied. However, while these techniques can achieve high sensitivity, fogging due to external pressure during handling and processing of photosensitive materials is remarkable, especially when rapid processing by an automatic developing machine is caused by pressure of transport rollers. Fogging failures such as streaks or black spots called roller marks are likely to occur. For example, it is difficult for medical photosensitive materials to be compatible with high image quality for improving diagnostic performance. Further, the silver halide photographic emulsion or a light-sensitive material containing the same has a drawback that photographic performance is significantly changed during storage after preparation, and improvement has been desired.

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SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity even in rapid processing, has less fog, has improved pressure resistance, and has little performance deterioration upon storage. Is to do.

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Means for Solving the Problems The present inventor has found that the following means are effective in improving the above-mentioned problems.

That is, (1) a method for producing a silver halide photographic emulsion wherein chemical sensitization is carried out in the presence of a compound represented by the general formula selected from the above [1] to [14]; Feeling
The chemical sensitization is carried out in the presence of a compound represented by the general formula [1], [3] or [14], wherein W is selected from a cyano group and a formyl group; Having a silver halide emulsion layer containing a silver halide photographic emulsion, developing, fixing,
3. A silver halide photographic light-sensitive material on which an image is formed through a water washing and drying step; and 3. a developing, fixing, water washing and drying step containing a compound represented by the general formula selected from the above [1] to [14]. A silver halide photographic light-sensitive material which forms an image via the following general formulas [1] and [3], wherein W is selected from a cyano group and a formyl group
Or containing the compound represented by [14].

Hereinafter, the present invention will be described in detail. First, the substituted alkene derivatives represented by the general formulas [1] to [14] will be described.

In the general formulas [1] to [14], W represents an electron-withdrawing group, D represents an electron-donating group, and H represents a hydrogen atom. The groups represented by W or D on the same carbon atom may form a cyclic structure with each other, and with respect to W or D, when either a trans structure or a cis structure is possible, either structure may be used. You may take it.

In the present invention, the general formulas [1] to [14]
The electron-withdrawing group represented by W is a substituent whose Hammett's substituent constant σp can take a positive value. Here, the Hammett's substituent constant σp is derived from an empirical rule for quantitatively discussing the effect of a substituent on the reaction or equilibrium of a benzene derivative, which is described in the column of Hammett's rule in the Iwanami Scientific Dictionary. It is. Specifically, a halogen atom, a cyano group, a nitro group, an alkenyl group, an alkynyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a carbamide group, a sulfamoyl group, Phenyl substituted with a sulfonamide group, a trifluoromethyl group, a trichloromethyl group, a phosphoryl group, a carboxy group (or a salt thereof), a sulfo group (or a salt thereof), a heterocyclic group, an imino group, or an electron-withdrawing group thereof. Group. These groups may have a substituent, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom),
Alkyl groups (including aralkyl groups, cycloalkyl groups, active methine groups, etc.), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, heterocyclic groups containing quaternized nitrogen atoms (eg, pyridinio groups), acyl Group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, Hydroxy group,
An alkoxy group (including a group containing a repeating ethyleneoxy or propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, a (alkoxy or aryloxy) carbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, an amino Groups, (alkyl, aryl or heterocycle) amino groups, N-substituted nitrogen-containing heterocyclic groups, acylamino groups, sulfonamide groups, ureido groups, thioureido groups, imide groups, (alkoxy or aryloxy) carbonylamino groups, sulfo groups Famoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio group, oxamoylamino group, (alkyl or aryl) sulfonyluureido group, acylureido group, acylsulfamoylamino group, Toro, mercapto, (alkyl, aryl or heterocycle) thio, (alkyl or aryl) sulfonyl, (alkyl or aryl) sulfinyl, sulfo or salts thereof, sulfamoyl, acylsulfamoyl, sulfonylsul Examples include a famoyl group or a salt thereof, a group having a phosphoric amide or a phosphoric ester structure, and the like. These substituents may further have a substituent.

The electron-withdrawing group is preferably a cyano group, a nitro group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group,
Substituted with a sulfamoyl group, a trifluoromethyl group, a phosphoryl group, a heterocyclic group (a 5- to 6-membered heterocyclic group, which may be condensed with a benzene ring or a naphthalene ring), or any electron-withdrawing group Phenyl group. However, the heterocyclic groups in the general formulas [3] and [7] are non-aromatic heterocyclic groups.

In the present invention, the general formulas [1] to [14]
The electron donating group represented by D is a substituent whose Hammett's substituent constant σp can take a negative value, and is an alkyl group,
Aryl group, hydroxy group (or salt thereof), mercapto group (or salt thereof), alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, aryl An amino group, a heterocyclic amino group, or a phenyl group substituted with these electron donating groups. These groups may have a substituent, and the substituent includes W
And the same ones.

The electron donating group is preferably an alkyl group, an aryl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an alkylthio group, an arylthio group, an amino group, an alkylamino group,
An arylamino group or a phenyl group substituted with an arbitrary electron donating group.

The ring formed by W and D is 4
A saturated or unsaturated carbocyclic or heterocyclic ring which may have a condensed ring of 6 to 6 members is mentioned, and a cyclic ketone may be used. The heterocyclic ring is preferably a heterocyclic ring containing at least one atom of N, O and S, more preferably one or two atoms.

Among the compounds represented by the general formulas [1] to [14], preferred compounds are those represented by the general formulas [1], [2],
[3], [5], [7], [8], [10], [1
1], [12], compounds represented by the general formulas [13] and [14], and more preferably the compounds represented by the general formulas [1] to [14].
[3], general formulas [5], [7], [8], [10],
[11] a compound represented by the general formulas [12] and [14], and particularly represented by the general formula [1], [3] or [14], wherein W is selected from a cyano group and a formyl group. Compound.

Next, specific examples of the compounds represented by the general formulas [1] to [14] are shown below. However, the present invention is not limited to these.

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The compounds of the present invention can be easily synthesized by known methods, and can also be purchased directly from drug manufacturers.

These compounds are dissolved in water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. Can be used.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used for dissolution and mechanical dissolution. An emulsified dispersion can be prepared and used. Alternatively, powders of these compounds can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves and used by a method known as a solid dispersion method.

In the present invention, (1) the chemical sensitization of a silver halide emulsion is carried out in the presence of these compounds;
(2) including the silver halide grains of (1) in a silver halide emulsion layer of a silver halide photographic light-sensitive material;
(3) The effect is exhibited by incorporating these compounds into the silver halide emulsion layer and / or other hydrophilic colloid layers of the silver halide photographic material.

These compounds may be used alone or in combination of two or more. It is preferable to add in the state as described above. The addition amount is preferably 1 × 10 ⁻⁶ mol to 1 mol, and more preferably 1 × 10 ⁻⁵ mol to 1 mol per mol of silver.
5 × 10 ⁻¹ mol is more preferred, and 2 × 10 ⁻⁵ mol to 2 ×
10 ^-1 mol is most preferred.

More preferably, the chemical sensitization of (1) is reduction sensitization. The term "presence" as used herein means a state in which the present compound is added before and after the addition of the chemical sensitizer. In particular, it is preferable to add the compound of the present invention after the addition of the reduction sensitizer. The term "after addition" includes the case where the reduction sensitizer and the compound of the present invention are added simultaneously. When a reduction sensitizer is used in combination with another chemical sensitizer, it is preferable that the reduction sensitizer is added before the addition of the compound of the present invention.

It is particularly preferable that (3) is contained in a silver halide emulsion layer. Of course, the silver halide photographic light-sensitive material of the present invention may be appropriately selected and used in combination with commonly known chemical sensitization methods such as sulfur sensitization, selenium or tellurium sensitization, reduction sensitization and noble metal sensitization. Good.

The noble metal sensitization is preferably gold sensitization, and a gold compound, mainly a gold complex such as a gold-thiocyanate complex is used as a sensitizer. As a noble metal other than gold, complex salts such as platinum, iridium, osmium, palladium, rhodium and ruthenium can be used. For gold sensitization, gold sensitizers such as chloroaurate, gold thiourea complex, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanouric amide, ammonium aurothiocyanate, pyridyl Trichlorogold and the like. The addition amount of these gold sensitizers can be varied over a wide range under various conditions.
It is preferably from 5 × 10 ⁻⁸ mol to 5 × 10 ⁻³ mol per mol, more preferably from 1 × 10 ⁻⁷ mol to 4 × 10 ⁻⁴ mol.

In the sulfur sensitization, examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount can be varied under various conditions, that is, in a wide range such as the size of silver halide grains, but as a guide, the amount is preferably 5 × 10 ⁻⁸ mol to 5 × 10 ⁻⁵ mol per mol of silver halide, and more preferably 1 × 10 ⁻⁵ mol. X 10 ^-7 mol to 1 X 10 ^-4 mol is preferred.

Further, selenium sensitization and / or tellurium sensitization are preferably used in combination. As the selenium sensitizer, a conventionally known compound can be used. That is, the emulsion is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain time.

Specific examples of unstable selenium sensitizers include
Isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (eg, 2-selenopropionic acid, 2-selenobutyric acid), selenoesters , Diacyl selenides (for example, bis-3-chloro-2,6-dimethoxybenzoyl selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like. Among them, triphenylphosphine selenide and the like are preferably used as a useful selenium sensitizer.

Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Those skilled in the art will recognize that an unstable selenium compound as a sensitizer for photographic emulsions is not very important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not critical. Is generally understood to have no role other than to carry selenium and make it present in the emulsion in an unstable form.

In the present invention, an unstable selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, and 2-alkyl selenide. Selenazolidinedione, 2-selenooxazolidinedione and derivatives thereof are mentioned.

The amount of the selenium sensitizer used depends on the amount of selenium used.
Depends on compound, silver halide grains, chemical ripening conditions, etc.
However, it is generally preferred that 1 ×
10 ^-8More than mole. More preferably 1 × 10^-7Mole
More than 1 × 10^-FourLess than mol is added during chemical sensitization. Attachment
The method of addition depends on the nature of the selenium compound used, such as water or water.
Or an organic solvent such as methanol or ethanol
Or by adding it after dissolving it in a mixed solvent,
And a method of preliminarily mixing and adding the solution.
Organic solvent, a method disclosed in JP-A-140739
Added in the form of an emulsified dispersion of a mixed solution with a soluble polymer
May be used.

Specific examples of tellurium sensitizers include colloidal tellurium, telluroureas (eg, allyl tellurourea,
N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N ', N'-dimethyltellurourea, N, N'-dimethylethylenetellurourea,
N'-diphenylethylene tellurourea), isotellurocyanates (e.g. allyl isotellurocyanate), telluro ketones (e.g. telluroacetone, telluroacetophenone), telluroamides (e.g. telluroacetamide, N, N-dimethyltellurobenzamide), tellurohydrazide (Eg, N, N ′, N′-trimethyltellurobenzhydrazide), telluroester (eg, t-butyl-t-hexyltelluroester), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropyl) Phosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride) and other tellurium compounds (for example, the negatively charged tellurium described in British Patent 1,295,462). Ion-containing gelatin, Potassium nitrosium telluride, Potassium nitrosium tellurocyanate diisocyanate, tellurocarbonyl penta isethionate, sodium salt, allyl tellurocyanate), and the like.

The amount of the tellurium sensitizer that can be used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, and the like, but is generally 10 ⁻⁸ mol to 10 ⁻ mol per mol of silver halide. ^{The amount} is preferably ² mol, more preferably about 10 ⁻⁷ mol to 5 × 10 ⁻³ mol. The conditions of the chemical sensitization are not particularly limited, but the pAg is preferably 6 to 11, more preferably 7 to 10,
The temperature is preferably 40 to 95C, more preferably 45 to 85C.

In the present invention, it is preferable to use noble metal sensitization and / or chalcogen sensitization and reduction sensitization in combination.

The reduction sensitization of the present invention is a method in which a reduction sensitizer is added to a silver halide emulsion, pAg1 called silver ripening.
Any of a method of growing or ripening in a low pAg atmosphere of 、 7 and a method of growing or ripening in a high pH atmosphere of pH 8 to 11 called high pH ripening can be selected. The addition method is a preferable method in that the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers include stannous salts, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide and dimethylaminoborane are preferred compounds as reduction sensitizers. Since the addition amount of these reduction sensitizers depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-8 mol to 10 ^-3 mol per mol of silver halide.

These reduction sensitizers are added after being dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides.

It is particularly preferred that the reduction sensitization of the present invention is carried out with ascorbic acid or one of its derivatives.

Ascorbic acid and its derivatives (hereinafter referred to as
It is called "ascorbic acid compound". The following can be mentioned as specific examples of ()). (A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) D-sodium ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-6-di Acetate (A-10) L-ascorbic acid-5,6-O-isopropylidene To add the above ascorbic acid compounds to the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion. Or a solvent such as water, methanol, ethanol or the like, alone or in a mixed solvent.

Ascorbic acid compound used in the present invention
Is an addition in which a conventionally known reduction sensitizer is preferably used.
It is desirable to use a large amount in comparison with the amount. For example, special public
Japanese Patent Application Laid-Open No. 57-33572 states that the amount of reducing agent
0.75 × 10 per gram^-2Milliequivalent (8 × 10^-FourMole
/ Ag × mol). 0.1 per kg of silver nitrate
mg to 10 mg (as ascorbic acid, 10 mg^-7Mo
10^-FiveMol / AgX mol) is often effective.
You. "US Patent No. 2,487,850 includes" Reduction sensitization.
The amount of tin compound that can be used as an agent is 1
× 10^-7Mol ~ 44 x 10^-6Mol ".
The ascorbic acid compound used in the present invention is an emulsion particle
Size, halogen composition, emulsion preparation temperature, pH, pAg
Although the preferred amount depends on factors such as
5 × 10 per mole of silver genide^-FiveMol ~ 1 x 10^-1Mole of
It is desirable to select from a range. More preferably 5 × 1
0 ^-FourMol ~ 1 x 10^-2Prefer to choose from a range of moles
No. Particularly preferred is 1 × 10^-3Mol ~ 1 x 10^-2Mole
Is to choose from the range.

The method of reduction sensitization using the ascorbic acid compound of the present invention can be combined with other methods of reduction sensitization.

In the present invention, the silver halide emulsion used can be spectrally sensitized. As the spectral sensitizing dye used in the present invention, usually a methine dye is preferably used, which includes a cyanine dye, a merocyanine dye,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes and the like are included.

For example, oxacarbocyanine, benzimidazolocarbocyanine, benzimidazolo-oxacarbocyanine and the like as described in JP-A-5-113619 are mentioned. In addition, Japanese Patent Application Laid-Open No. 6-332102
Dyes having a sensitizing effect in the blue light region described in the above publication are also preferably used. These spectral sensitizing dyes can be used alone or in combination.

The spectral sensitizing dye is preferably added as a solution dissolved in an organic solvent such as methanol or as a dispersion of solid fine particles.

The amount of the spectral sensitizing dye to be added is not uniform depending on the kind of the dye and the emulsion conditions.
0 mg to 900 mg is preferable, and 60 mg to 400 mg
Is particularly preferred.

The spectral sensitizing dye is preferably added before the end of the chemical sensitization, and may be added in several portions before the end of the chemical sensitization. More preferably, after the completion of the growth of the silver halide grains and before the end of the chemical sensitization, particularly preferably before the start of the chemical sensitization.

To stop the chemical sensitization (chemical ripening) in the practice of the present invention, a method using a chemical ripening terminator is preferable in consideration of the stability of the emulsion and the like. Examples of the chemical ripening inhibitor include halides (eg, potassium bromide, sodium chloride, etc.), and organic compounds known as antifoggants or stabilizers (eg, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene). These can be used alone or in combination of a plurality of compounds.

The light-sensitive material of the present invention is a light-sensitive material having a light-sensitive silver halide emulsion layer on at least one side of a support. The light-sensitive material comprises a support having a subbing layer coated thereon as a photographic component layer, for example, a photosensitive emulsion layer, and a hydrophilic colloid layer thereon, such as an intermediate layer, a protective layer, and an antistatic layer. This is the configuration applied above.
As a preferred embodiment of the present invention, a crossover cut layer, a photosensitive silver halide emulsion layer,
An intermediate layer is provided thereon as a hydrophilic colloid layer, and a protective layer is provided on the uppermost layer.

The binder preferably used in the silver halide photographic light-sensitive material of the present invention is dextrin, polyvinyl alcohol,
Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide,
Various kinds of synthetic hydrophilic polymer compounds such as a single or copolymer of polyvinylimidazole can be used.

Examples of gelatin include lime-processed gelatin, Bull. Soc. Photo. Japan, 16,
Acid-treated gelatin described on page 30 (1966) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used.

Examples of the gelatin derivative include various types of gelatin such as acid halides, acid anhydrides, isocyanates, alkane sultone bromoacetates, vinylsulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds and the like. Examples thereof include those obtained by reacting a compound.

Of these, dextran and / or polyacrylamide are preferably used together with gelatin. The coating amount of the hydrophilic binder is 3.8 to 1.0 g / m ² per one side, preferably 3.5 to 1.0 g / m ^2.
1.5 g / m ² .

The light-sensitive silver halide emulsion of the silver halide photographic light-sensitive material of the present invention may be silver bromide, silver iodobromide, or a silver iodochlorobromide emulsion containing a small amount of silver chloride.

The emulsion used in the silver halide photographic light-sensitive material of the present invention contains tabular silver halide grains described later, and the silver halide grains themselves are known.
It can be manufactured by a known method.

The particle size distribution of the silver halide grains may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may have a different silver halide composition between the inside and the outside. For example, a high silver iodide core portion is coated with a low silver iodide shell layer to form a clear two-layer structure. The core / shell type monodisperse emulsion may be used.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. Monodisperse here means, when the average particle diameter is measured by an ordinary method,
Silver halide grains in which at least 95% of the grains by number or mass are within ± 40%, preferably within ± 30% of the average grain size.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be obtained by, for example, using a seed crystal as a method for obtaining a monodisperse emulsion and supplying silver ions and halide ions using the seed crystal as a growth nucleus. Emulsions may be used.

In the silver halide photographic light-sensitive material of the present invention, the average grain size of usable silver halide grains is 0.95.
μm or less, particularly 0.25 to 0.6
0 μm particles are preferred. The shape of the silver halide grains is not particularly limited, and may be any of a flat plate shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedral shape, and any other shapes.

Further, a narrower particle size distribution is preferable, and a so-called monodispersed emulsion in which 90%, preferably 95% of the total number of particles fall within a particle size range of ± 40% of the average particle size is particularly preferable.

The emulsion used in the silver halide photographic light-sensitive material of the present invention preferably has an aspect ratio (grain size / grain thickness) of 70% or more, more preferably 90% or more, of the total projected area of the silver halide emulsion layer. Ratio) is a tabular grain having a ratio of 3 or more and 20 or less, preferably an aspect ratio of 4 or more and 1 or less.
0 or less silver halide grains.

The advantages of the tabular silver halide grains are that, for example, British Patent No. 2,11 discloses that the spectral sensitization efficiency and the graininess and sharpness of an image can be improved.
No. 2,157, U.S. Pat. Nos. 4,414,310 and 4,434,226, and emulsions can be prepared by referring to the methods described in these publications.

The method of reacting the soluble silver salt and the soluble halogen salt in the emulsion preparation method may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof.

A method of forming silver halide grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. A method of maintaining a constant pAg in a liquid phase in which silver halide is formed, as one type of the double jet method;
That is, a so-called controlled double jet method can be used. According to this method, silver halide grains having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion is formed in at least one of the steps of forming or growing grains by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, ruthenium salt, osnium salt, iron Salt, copper salt,
It is preferable to add a complex salt containing an element of Groups 3 to 13 of the periodic table, such as a platinum salt or a palladium salt.

The ligands of these complex salts include a halogen atom, a nitrosyl group, a cyano group, an aquo group, an alkyl group,
A pseudohalogen group, an alkoxy group, an ammonium group, and any combination thereof can be used.

The surface of the silver halide grains can be controlled in halogen composition by using water-soluble halides or silver halide fine grains. This technique is known in the art as conversion and is widely known.

The silver halide grains may be uniform from the inside to the surface, or may be composed of a plurality of layers having different halogen compositions, dopant species and amounts, distribution of lattice defects, and the like.

The emulsion may be subjected to a water washing method such as a Nudel washing method or a flocculation sedimentation method in order to remove soluble salts. As a preferred water washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group, or a method using a polymer flocculant or the like is mentioned as a particularly preferable desalting method.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (RD).
No. 17643, (December 1978) 22-23
It is described in the literature described on the page or cited.

In the light-sensitive material of the present invention, the coated amount of silver halide grains is preferably 0.5 to 2.25 g / m ² per side, more preferably 0.5 to 2.0 g / m 2.
² It is preferable that the amount of silver added is in this range in order to obtain the effects of the present invention.

The silver halide photographic light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. it can. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole)
Mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione, azaindenes; such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3,3
a, 7-tetrazaindenes), pentazaindenes, etc., benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers, such as benzenesulfonamide, potassium bromide and the like, can be added. Particularly preferably, N, O, S, Se
Or a substituted or unsubstituted heterocyclic or fused heterocyclic ring, or a water-soluble halide.

The photosensitive emulsion layer and the non-photosensitive hydrophilic colloid may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'- Methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) isoxazole , Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, isocyanates, carboxyl group-activated hardeners and the like can be used alone or in combination.

The preferable addition amount of these hardeners slightly varies depending on the addition amounts and types of gelatin, latex and other binder materials.
0.0 mmol. More preferably 0.05 to
1.0 mmol.

The emulsion layer and / or the non-photosensitive hydrophilic colloid layer may contain various known surfactants for various purposes such as coating aid, antistatic, improvement of slipperiness, emulsification / dispersion, prevention of adhesion and improvement of photographic properties. An agent may be used.

The photosensitive material used in the present invention contains various other additives. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, colloidal silica, and the like can be used.

The additives described above are specifically described as follows.
(RD) No. 17643 (December 1978), N
o. 18716 (November 1979) and 308
119 (December 1989) can be used.

In the light-sensitive material of the present invention, the photographic constituting layer is coated on one or both sides of a flexible support usually used for the light-sensitive material. Useful as flexible supports are films of synthetic polymers of cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polyethylene terephthalate (which may contain colored pigments) or polyethylene or Paper supports and the like coated with a polymer such as polyethylene terephthalate. These supports may have a magnetic recording layer, an antistatic layer, and a release layer.

In the present invention, the method for coating the emulsion layer, the surface protective layer and the like on the support is not particularly limited,
For example, US Patent Nos. 2,761,418 and 3,50
Nos. 8,947 and 2,761,791 can be used.

Next, the processing method of the present invention will be described. In the developer, JP-A 6-1 as a developing agent is used.
In addition to dihydroxybenzenes, aminophenols and pyrazolidones described in JP-A-38591 (pages 19 to 20), reductones described in JP-A-5-165161 are also preferably used. Of the pyrazolidones used, those in which the 4-position is particularly substituted (dimesone, dimesone S, etc.) are particularly preferred because they are less soluble in water and have less change with time of the solid treating agent itself. As the preservative, an organic reducing agent can be used in addition to the sulfite. In addition, bisulfite adducts of chelating agents and hardeners can be used. JP-A-5-289255, JP-A-6-308
It is also preferable to add a compound described in No. 680 (general formulas [4-a] [4-b]). The addition of a cyclodextrin compound is also preferable, and the compounds described in JP-A-1-124852 are particularly preferable.

An amine compound can be added to the developer, and the compounds described in US Pat. No. 4,269,929 are particularly preferred. Further, it is necessary to use a buffer, and as the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate,
Potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5-sulfo Sodium salicylate), 5-sulfo-2
Potassium-hydroxybenzoate (potassium 5-sulfosalicylate);

Examples of development accelerators include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, amine compounds, polyalkylene oxides, 1-phenyl-3-pyrazolidones, hydrazines, ionic compounds, Mesoionic compounds, imidazoles and the like can be added as needed.

As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
-Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-
Examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindene and adenine, and typical organic antifoggants include 1-phenyl-5-mercaptotetrazole.

Further, if necessary, methyl cellosolve,
Methanol, acetone, dimethylformamide, cyclodextrin compound, and other JP-B-47-33378
And the compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent. Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkali metal such as KBr, an organic inhibitor, and a development accelerator are used.

Known compounds such as a fixing agent, a chelating agent, a pH buffer and a balancing agent can be used in the fixing solution. For example, JP-A-4-242246 or JP-A-5-11363 can be used.
No. 2 can be used.

As the fixing agent, thiosulfate, thiocyanate and the like are used, and may further contain a preservative, a pH adjuster, a water softener and the like.

The silver halide photographic light-sensitive material of the present invention is preferably supplied while continuously processing a solid processing agent.
Here, the solid processing agent is a powder processing agent, a solid processing agent such as tablets, pills, granules, and the like, and examples thereof include those subjected to moisture proof processing as needed. The powder refers to an aggregate of fine particle crystals. Granules are obtained by adding a granulation step to powder, and refer to granules having a particle size of 50 to 5000 μm, and tablets refer to powder or granules obtained by compression molding into a certain shape.

As a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet,
3-137793, 63-97522, Kaikai 1
There is a known method such as JP-85732, but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum.

When the solid processing agent is in the form of granules or powders, see JP-A-62-81964 and JP-A-63-8415.
No. 1, Japanese Patent Laid-Open No. 1-292375, and a method using a screw or a screw described in Japanese Utility Model Application Laid-Open Nos. 63-105159 and 63-195345 are known as known methods. Can be processed.

The place where the solid processing agent is charged may be any place in the processing tank, but is preferably a place where the processing liquid is communicated with the processing section for processing the photosensitive material and the processing liquid flows between the processing section and the processing section. In addition, a structure is preferable in which there is a constant circulation amount of the processing liquid between the processing unit and the dissolved component moves to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

In the present invention, the processing temperature in each step is preferably 25 to 50 ° C. for a developing solution, and more preferably 30 to 4 ° C.
0 ° C. Fixing solution at 20 to 50 ° C., preferably 30 to
40 ° C. Washing (stabilization) is performed at 0 to 50 ° C, preferably 15 to 40 ° C. Drying is performed at 35 to 100 ° C, preferably 40 to 80 ° C.

The photographic material of the present invention is preferably dried after squeezing with a squeeze roller after development, fixing and washing (or stabilization) with water.

In the processing method of the present invention, it is preferable that after the imagewise exposure of the photographic material, the photographic material is processed under the conditions satisfying the following formula.

L ^0.75 × t = 40 to 130 (0.7 ≦ L ≦ 4.0) (where L is the contact point between the first roller pair at the film insertion port of the automatic processor and the last roller pair at the film drying port) Represents the length (unit: m) of the transport path to the contact point, and t represents the time (unit: second) required to pass through L. Here, the processing length L at the time of processing is 0 The range of more than 0.7 and less than 4.0 (unit) is preferable. When L is less than 0.7, each processing step is small, and sensitivity and / or contrast is reduced. Further, since the number of transport rollers is reduced, transportability is deteriorated.

When L is larger than 4.0, the conveying speed becomes too slow, and the photosensitive material is undesirably scratched.

The product of L ^0.75 and t is preferably 40 or more and 130 or less. If this value is less than 40, sensitivity and contrast are lowered, and problems such as poor drying are caused. L ^0.75 is more preferably 45 or more, and if it exceeds 130, it goes against the current situation where rapid processing is desired, which is not preferable.

[0125]

[A1]

Ossein gelatin 24.2 g Distilled water 9657 ml Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% methanol aqueous solution) 6.78 ml KBr 10.8 g 10% AgNO ₃ 114 ml [B1] 2.5N AgNO ₃ aqueous solution 2825 ml [C1 841 g of KBr and finished to 2825 ml with water [D1] 1.75 N KBr aqueous solution The following silver potential control amount at 42 ° C: JP-B-58-58288 and 58-5828
Using a mixing stirrer described in the specification of No. 9, 464.3 ml of each of the solution B1 and the solution C1 was added to the solution A1 by a simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, it took 40 minutes to raise the temperature of the solution A1 to 50 ° C., and the pH was adjusted to 5.0 with 3% KOH. The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 42 ° C. to 50 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.045 μm. It was confirmed by an electron microscope that the average particle size (circular diameter conversion) was 0.42 μm. The variation coefficient of the thickness was 42%, and the variation coefficient of the distance between twin planes was 45%. <Preparation of tabular silver bromide emulsion> Seed emulsion-1 and 3 shown below
A tabular pure silver bromide emulsion was prepared using the seed solutions. [A2] Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous methanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3669 ml with water [B2] KBr 1747 g with water Finish to 3669 ml [C2] AgNO ₃ 2493 g Finish to 4193 ml with water Keep solution A2 at 50 ° C in a reaction vessel, stir vigorously, and add the total amount of solution B2 and solution C2 to the mixture over 100 minutes by simultaneous mixing method did. During this time, the pH was kept at 9.0 with the KOH solution, and the pAg was kept at 8.6 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed functionally with respect to time so as to match the critical growth rate. That is, they were added at an appropriate addition rate so that no small particles were generated except for the seed particles that were growing, and that they did not become multicomponent due to Ostwald ripening.

After the addition was completed, the emulsion was cooled to 40 ° C.
As an aggregating polymer agent, 1800 ml of an aqueous solution of 13.8% (by mass) of modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added and stirred for 3 minutes. afterwards,
An aqueous solution of acetic acid 56% (mass) was added to adjust the pH of the emulsion to 4.
After stirring for 3 minutes, the mixture was allowed to stand for 20 minutes, and the supernatant was drained by decantation.
After 5 l of the mixture was added and the mixture was stirred and allowed to stand, the supernatant was drained.

Subsequently, an aqueous solution of gelatin and sodium carbonate 1
A 0% (mass) aqueous solution was added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, it was found that the average grain size was 0.84 μm, the average thickness was 0.16 μm, the average aspect ratio was about 5.3, and the grain size distribution was 20%. Tabular silver halide grains were obtained. The amount of gelatin at the end of physical ripening was 15.9 g per mol of silver halide. <Sensitization of silver halide> After the above-prepared emulsion was heated to 55 ° C, 450 mg of the following spectral sensitizing dye (A) and 45 mg of the following spectral sensitizing dye (B) were added per 1 mol of silver halide. ) Further, 4-hydroxy-6-methyl-1,
100m of 3,3a, 7-tetrazaindene (TAI)
g was added. After 10 minutes, (step) 3.5 mg of chloroauric acid, 10 mg of sodium thiosulfate and 100 mg of ammonium thiocyanate were added. After a further 40 minutes, 0.3 mol of the following silver iodide fine grains were added (step). After a further 10 minutes, 5 mg of triphenylphosphine selenide was added, and after a further 40 minutes (TAI) was adjusted to 500.
mg, and after 5 minutes, 13 g of trimethylolpropane,
After adding 30 g of gelatin (step), the emulsion was rapidly cooled to gel the emulsion to complete the sensitization. Further, L-ascorbic acid was used as a reduction sensitizer in an amount of 1.8 × 1 per mol of silver.
0 ^-3 mol of the emulsion was added after the temperature of the emulsion was raised to 55 ° C. to prepare an emulsion which was subjected to reduction sensitization. The general formulas [1] to [1]
The addition position of the compound represented by [4] is appropriately selected from the steps. (Spectral sensitizing dye) Sensitizing dye (A): 5,5'-di-chloro-9-ethyl-
Anhydride of sodium 3,3'-di- (3-sulfopropyl) oxacarbocyanine Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3 Anhydrous sodium salt of '-di- (4-sulfobutyl) benzimidazolocarbocyanine <Preparation of silver iodide fine particles> [A3] Ossein gelatin 100 g KI 8.5 g Make up to 2000 ml with distilled water [B3] 360 g of AgNO ₃ Make up to 605 ml with distilled water [C3] KI 352 g Make up to 605 ml with distilled water Add solution A3 to a reaction vessel, stir at 40 ° C., and stir at a constant speed for 30 minutes by simultaneous mixing of solution B3 and solution C3. Was added. The pAg during the addition was kept at 13.5 by a conventional pAg control means. The formed silver iodide was a mixture of β-AgI and γ-AgI having an average grain size of 0.06 μm. This emulsion is called a silver iodide fine grain emulsion. <Preparation of Subbed Support> A corona discharge treatment of 8 W · min / m ² was applied to both sides of a polyethylene terephthalate (PET) base having a thickness of 175 μm and colored blue at a concentration of 0.17. Apply lower layer, 110
Dried at ℃ for 1 minute. Then, after performing the same corona discharge treatment again, the following undercoating upper layer coating solution was applied,
After drying at 0 ° C. for 1 minute, a subbed support was obtained. (Undercoat lower layer) Latex: St (15), EA (85) 200 mg / m ² Compound A 5.0 mg / m ² Hexamethylene-1,6-bis (ethyleneurea) 5.0 mg / m ² (Undercoat upper layer) ) N-butyl acrylate (10), t-butyl acrylate (35), styrene (25), hydroxyethyl methacrylate (30) 10 mg / m ² compound L-1 30 mg / m ² compound A 5.0 mg / m ² acetic acid 2 .0mg / m ² average silica 3.0 mg / m ² compound of particle size 3μm S 5.0mg / m ²

[0131]

Embedded image

Next, the following additives were added to each of the sensitized emulsions to prepare a photosensitive silver halide emulsion coating solution.
Additives are as follows, and the amount of addition is shown per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 70 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.0 g nitrophenyl-triphenyl Phosphonium chloride 5 mg 2-anilino-4,6-dimercaptotriazine 10 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 2 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1- Phenyl-5-mercaptotetrazole 15 mg 2-mercaptobenzimidazole-5-sodium sulfonate 8 mg Dextran (average molecular weight: 40,000) 1.2 g Colloidal silica (Ludox AM particle size 0.013 μm manufactured by DuPont) 10 g Compound of the present invention Quantity on table

[0134]

Embedded image

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-di- (n-hexyl) -sulfosuccinate 1 g Polymethyl methacrylate (a matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide (area average particles) diameter 1.2μm matting _{agent) 0.5g C 7 F 15 CH 2} - (OCH 2 CH 2) 13 -OH 2mg 1,2- di (vinylsulfonyl acetamide) ethane (hardening agent) 1.2 g the protection simultaneously A layer coating solution was also prepared.

The additives used in the protective layer solution are as follows, and the amount of addition is shown in terms of 1 L of the coating solution.

[0137]

Embedded image

The obtained emulsion coating solution and protective layer coating solution were
The amount of silver in the emulsion layer was 4.4 g based on a blue-colored 175 μm thick undercoated polyethylene terephthalate film base previously coated with the following back layer on the opposite side of the emulsion layer.
/ M ² , the amount of the emulsion coating solution with gelatin was 4.0 g.
/ M ^2, using a slide hopper type coater so that the 1.15 g / m ² as a gelatin protective layer, min 85
m at the same time on the support to produce the indicated samples.

The additives used for the back layer are as follows, and the additives are shown in an amount per liter of the coating solution.

Incidentally, the amount of gelatin added to the back layer was 5 g / g.
It was applied as a m ^2. Lime-treated inert gelatin 68g

[0141]

Embedded image

[0142]

Embedded image

Polymethyl methacrylate (matting agent having an area average particle size of 5 μm) 1.1 g Silicon dioxide (matting agent having an area average particle size of 1.2 μm) 0.5 g 1,2-di (vinylsulfonylacetamide) ethane (hard film) Agent) 0.6 g Sodium chloride 0.1 g The properties of the obtained sample were evaluated using the following treatment solutions.
<Developing treatment> The developing treatment was performed by Dry to Dry in 45 seconds using an automatic developing machine SRX-701 (manufactured by Konica Corporation).

The replenishment amounts of the developing solution and the fixing solution are four cuts (2
(5.4 cm × 30.5 cm) It was set to 14 ml per sheet. <Preparation of solid developer> [Granulated product (A)] 1050 g of sodium metabisulfite,
450 g of 1-phenyl-3-pyrazolidone, 7200 g of sodium erysorbate monohydrate, 810 g of binder D-sorbit, 7 g of N-acetyl-DL-penicillamine
Is mixed at room temperature for about 3 minutes in a commercially available stirring granulator,
After granulating by adding 0 ml of water over 1 minute, the granulated material is dried at 50 ° C. for 2 hours in a fluidized bed drier to remove the moisture of the granulated material almost completely. [Granulated material (B)] An average of 10500 g of potassium carbonate and 6.0 g of potassium iodide were averaged in a commercially available bantam mill.
Grind to μm. These fine powders and DTPA-N
a 170 g, sodium sulfite 425 g, 5-mercapto- (1H) -tetrazolylacetic acid Na 8.3 g, 1-
(3-Sulfophenyl) -5-tetrazole-Na40
g, binder mannitol 1500 g, D-sorbit 6
After mixing for about 3 minutes at room temperature in a commercially available stirring granulator and adding 125 ml of water over 1 minute to granulate, the granulated product is dried at 40 ° C. in a fluidized dryer at 40 ° C. for 2 minutes. After drying for a time, the water content of the granules is almost completely removed.

The granulated product (A) thus obtained was
1.0% of the total mass of sodium octanesulfonate,
In a room conditioned at 25 ° C. and 40% RH or less, the mixture is further mixed. Further, sodium 1-octanesulfonate is added to the granulated product (B) at 1.2% of the total mass at 25 ° C. and 40% RH or less. The mixture was added and mixed in a wet room, and compression tableting was performed using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho to produce each of the developed tablets (A) and (B). In addition, 1
Filling amount per tablet is (A) 8.45 g, (B) 12.4 g
I made it. 60 tablets of (A) and 50 pieces of (B) (the volume after dissolution becomes 5.0 L) were sealed and packaged with a packaging material having the following layer constitution for moisture prevention.

The packaging material is biaxially stretched nylon (ONY)
15 μm thickness / aluminum oxide deposited PET 12 μm thickness /
A bag made of a laminate material consisting of biaxially oriented polypropylene (OPP) 25 μm thick / low-density polyethylene (LLDP) 40 μm thick. The effective surface area on the side (inside) of the packaging material in contact with the tablets was 1300 cm ² . . <Preparation of solid fixing agent> [Granulated product (C)] In a commercially available bantam mill, 14580 g of ammonium thiosulfate / sodium thiosulfate (90/10 mass ratio) is pulverized to an average of 10 µm. Compound (O1) (HO—CH ₂ CH ₂ —S—CH ₂ C
_{H 2 -S-CH 2 CH 2} -OH) 1000g, sodium metabisulfite 920 g, 5-mercapto - tetrazole 50 g, binders PINEFLOW 900g was added, mixed for about 3 minutes at room temperature in a commercial stirring granulator Then, after granulating by adding 150 ml of water over 1 minute, the granulated material is dried at 40 ° C. with a fluidized bed drier to remove water almost completely. [Granulated product (D)] 250 g of boric acid, 1500 g of aluminum sulfate octahydrate, 1150 g of succinic acid, 250 g of tartaric acid, 208 g of mannite, and 100 g of D-sorbite are added, and the mixture is added at room temperature in a commercially available stirring granulator. Mix for 3 minutes, 150ml
Of water is added over 1 minute to granulate, and the granulated material is dried at 40 ° C. in a fluidized bed drier to remove water almost completely.

The granulated product (C) thus obtained, 1400 g of sodium acetate and sodium 1-hexanesulfonate in a room conditioned at 2.5% of the total mass, 25 ° C. and 40% RH or less. 1400 g of sodium acetate was added to the granulated product (D), and sodium 1-hexanesulfonate was further added to 3.0% of the total mass at 25 ° C and 40%.
The mixture was added and mixed in a room humidified to RH or less, and compression tableting was performed using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to produce fixing tablets (C) and (D). The filling amount per tablet is (C) 10.5 g,
(D) The weight was 8.95 g. This is (C) 92 pieces, (D)
Twenty-eight tablets (volume having a volume after dissolution of 5.0 L) were sealed and packaged using the packaging material used for developing tablets (A) and (B) for moisture prevention. Development starter formulation (addition amount to 1 L of developer) N-acetyl-DL-penicillamine 0.11 g Diethylene glycol 48.5 g Compound (O1) 0.07 g 5-mercapto- (1H) -tetrazolylacetic acid Na 0.12 g Acetic acid 90% 11 5.5 g KBr 8.0 g Finished with pure water 67 ml A large-scale automatic developing machine SRX-701 (manufactured by Konica Corporation) was modified to incorporate a chemical mixer for tablet dissolution. As the developing solution in the developing tank at the start, 13.7 L of the developing solution in which the developing tablet was dissolved was added, a starter was added thereto, and the processing was started by filling the developing tank as a starting solution. The amount of the starter added is 67 ml / l liter of developer and the capacity of the developing tank is 13.7 liter
The appropriate amount was added. Fixing solution 1 prepared similarly
3.7 L of the starting solution was placed in the fixing processing tank of SRX-701.

In each of the developing and fixing steps, each of the packaging bags was opened by hand at the inlet of each solid agent, and the tablets were dropped into the built-in chemical mixer.
(0 ° C) and dissolving with stirring for 25 minutes while stirring and dissolving.
Adjust to 0L. This was used as a developing and fixing replenisher.

The pH when the developer was dissolved was 10.15,
The pH when the starter was added was 9.90. The dissolution pH of the fixing solution was 4.25.

The built-in chemical mixer is divided into a liquid preparation tank and a spare tank tank. The capacity of the liquid preparation tank is 5.0 L, and the capacity of the spare tank is 5.0 L. The film was prepared in the liquid preparation tank during running processing of the film. A spare tank was provided so that the replenisher was supplied so that the replenisher would run out during the stirring and dissolving time (about 25 minutes) even if the replenisher was exhausted.

Processing was performed at a developing temperature of 35 ° C., a fixing temperature of 35 ° C., a rinsing temperature of 18 ° C., and a drying temperature of 45 ° C., and the following was evaluated. <Evaluation of sensitometry (photographic performance)> An aluminum wedge was applied to the obtained sample through an intensifying screen (manufactured by Konica Corporation; M-100) using an X-ray generator MGU-10C manufactured by Toshiba Corporation. Tube voltage 27 kVp, tube current 100 mA,
X-rays were irradiated for 0.5 seconds. After the irradiation, development was performed under the above-mentioned processing conditions, and sensitivity and fog were measured as sensitometric evaluation.

The sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog + 0.5. The relative sensitivities are shown assuming that the sensitivity of 1 is 100. The measurement of the concentration was performed using a concentration meter PDA-65 manufactured by Konica Corporation. <Evaluation of pressure resistance (roller mark)> In this evaluation, each sample was subjected to X-ray exposure so that the concentration became 1.2 ± 0.5, and then the above-described treatment was performed. However, the developing rack of the automatic developing machine used and the transition rack from development to fixing were those which were intentionally fatigued. That is, due to fatigue of the rollers of each rack, irregularities of about 10 μm were formed on the entire surface. A large number of fine spot-like density unevenness was generated in the sample having poor pressure resistance due to the pressure caused by the unevenness in the sample after the treatment. This level was visually evaluated according to the following criteria.

A: No spots were generated. B: Small spots were generated. C: Many spots were generated. <Evaluation of storage stability (sensitivity / fog)>
40% RH at 55 ° C. for 3 days, and 80% RH, 23
After storage at ℃ for 3 days, the sensitivity and fog were measured and evaluated in the same manner as in the evaluation of sensitometry.

The above results are shown in Tables 1 and 2.

[0155]

[Table 1]

[0156]

[Table 2]

[0157]

According to the silver halide photographic light-sensitive material of the present invention, even in rapid processing, high sensitivity, little fog, improved pressure resistance, and excellent storage stability are obtained.

Claims (6)

[Claims] 1. A method for producing a silver halide photographic emulsion, wherein the chemical sensitization is carried out in the presence of at least one compound represented by the general formula selected from the following [1] to [14]: . Embedded image [Wherein, W is an electron-withdrawing group, D is an electron-donating group, H
Represents a hydrogen atom. W or D on the same carbon atom
The groups represented by may form a cyclic structure with each other, and may have either of a trans structure and a cis structure with respect to W or D when possible. ] 2. The method for producing a silver halide photographic emulsion according to claim 1, wherein said chemical sensitization is reduction sensitization. 3. The method according to claim 1, wherein the chemical sensitization is performed in the presence of a compound represented by the general formula [1], [3] or [14], wherein W is selected from a cyano group and a formyl group. Item 3. The method for producing a silver halide photographic emulsion according to Item 1 or 2. 4. An image forming method comprising a silver halide emulsion layer containing a silver halide photographic emulsion produced by the production method according to claim 1, 2 or 3, and a developing, fixing, washing and drying steps. A silver halide photographic light-sensitive material, characterized in that: 5. A silver halide photograph containing a compound represented by the general formula selected from the above [1] to [14] and forming an image through development, fixing, washing and drying steps. Photosensitive material. 6. The silver halide according to claim 5, wherein W contains a compound represented by the general formula [1], [3] or [14] selected from a cyano group and a formyl group. Photosensitive material.