JP2000155382A - Silver halide photographic sensitive material and method for processing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material high in sensitivity and small in fog even in rapid processing and improved in pressure resistance and small in fluctuation of processing and to provide the method for processing it. SOLUTION: This photosensitive material contains at least one of silver halide emulsions which is prepared by growing silver halide grains, while properly extracting an aqueous solution containing salts out of a reactant solution by using an ultra-filtration method and it contains a compound represent by the formula in which each of R11 and R15 is, independently, an optionally substituted 1-5C alkyl or optionally substituted alkoxy or cyano group; and each of R12-R14 is, independently, an H atom a carboxy, sulfo or phosphoric group or a 1-4C alkyl or alkenyl group substituted by a carboxy, sulfo, sulfuric, or phospho group, but each of R12-R14 is not an H atom at the same time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material (hereinafter simply referred to as "photosensitive material") and a processing method thereof. More specifically, the present invention relates to a silver halide photographic light-sensitive material having high sensitivity, low fog, excellent graininess, pressure resistance, and processing dependency, and a processing method therefor.

[0002]

2. Description of the Related Art In recent years, advances in electronics have dramatically shortened access times to images, and silver halide photographic materials have been required to be processed more and more rapidly. Further, a technique for improving the image quality (granularity, sharpness) of an image is desired, and further finer silver halide grains are required. Higher sensitivity is required to make silver halide grains finer, and various sensitization techniques have been studied so far. For example, high sensitivity has been achieved by chemical sensitization such as chalcogen sensitization method using selenium or tellurium compound. However, generation of fog caused by external pressure during handling and processing of photosensitive material There are drawbacks such as the occurrence of image formation and a large change in gradation due to a change in development processing temperature by an automatic developing machine, and improvement has been desired.

Among techniques for improving silver halide emulsions for the purpose of improving the sensitivity and image quality of silver halide photographic materials,
One of the most basic and important techniques is a technique for monodispersing a silver halide emulsion. Since the optimal conditions for chemical sensitization and color sensitization are different between large and small silver halide grains, the chemical sensitization and color sensitization are optimal for a mixed silver halide emulsion with a wide grain size distribution. It is difficult to perform sensitization, and as a result, fog is increased or sufficient chemical sensitization cannot be performed in many cases. On the other hand, in the case of a monodisperse (narrow size distribution) silver halide emulsion, it is easy to perform optimal chemical sensitization and color sensitization, and it is highly sensitive, has low fog, and has excellent graininess. It becomes possible to prepare a silver emulsion.

As a technique for monodispersing tabular silver halide grains, Japanese Patent Application Laid-Open No. 1-213637 discloses a monodisperse silver halide grain having two parallel twin planes to improve sensitivity and graininess. The technology is described. JP-A-5-173268 and JP-A-6-202258 disclose a method for producing a tabular silver halide emulsion having a small particle size distribution. However, the monodispersed tabular silver halide grains to which the above technique is directed are silver halide grains in which the variation in the area-converted grain size between individual grains is small.
Incidentally, the size of tabular grains is determined from two parameters.

One is the area-converted particle size of tabular grains,
The other is the thickness of tabular grains. That is, even if only the area-converted particle size distribution of the tabular grains is reduced, the size distribution of the tabular grains cannot be reduced. When the size distribution of the tabular grains is wide, problems such as variation in sensitivity and granularity deterioration due to differences in developability occur.

In Japanese Patent Application Laid-Open No. 6-258744, monodisperse tabular silver halide grains having an aspect ratio of 2 or more having regions having different silver halide compositions inside grains are used to obtain sensitivity, gradation, pressure resistance, latent image, and the like. Techniques for improving image storability have been reported. Monodisperse silver halide grains as referred to in this technique means that the dispersion of the volume-converted grain size among the individual grains is small. However, the above technique does not include a technique for improving the production cost of a tabular silver halide emulsion. JP-A-5-210188 discloses that
A core containing 45 mol% of silver iodide was mixed with an intergrain distance of 0.1%.
There is disclosed a technique of forming under a condition of about 3.0 μm (although the definition of the distance between particles is different, the value obtained by dividing the value of “distance between particles” in the publication by 0.89 is almost the same as that in the present invention. "Average distance between particles"). However, this technique does not intend to arbitrarily control the average intergranular distance in the grain growth process, and has no specific means therefor.

[0007] In developing silver halide photographic emulsions, not limited to tabular silver halide emulsions, there is an important viewpoint other than performance in terms of production cost. An effective method in terms of production cost is to increase the amount of emulsion produced at one time, in other words, to increase the yield of silver halide at the end of grain growth in a reaction vessel for preparing a silver halide emulsion. I do. That is, the concentration of silver halide in the emulsion at the end of grain growth is increased, and a direct method is concentration of the silver halide emulsion.

As a method for concentrating the volume of the reaction product (silver halide emulsion) in the emulsion preparation step, a technique using an ultrafiltration method is disclosed in JP-B-59-43727 or JP-A-3-14094.
No. 6, etc. However, these methods do not include suggestions on how to prepare tabular grains or even monodispersed tabular silver halide emulsions. Further, it is not intended to control the average intergranular distance of silver halide grains when preparing a silver halide emulsion.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, reduced fog, improved pressure resistance, and reduced processing fluctuation, and a processing method therefor. .

[0010]

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

(1) At least one type of silver halide emulsion produced by ultrafiltration at the time of silver halide grain formation while conducting grain growth while appropriately extracting an aqueous solution containing a salt from a reaction solution, A silver halide photographic material comprising a compound represented by the following general formula (1).

[0012]

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[Wherein R ₁₁ and R ₁₅ each independently represent an alkyl group having 1 to 5 carbon atoms, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, or a cyano group. R ₁₂ , R ₁₃
And R ₁₄ are each independently a hydrogen atom, a carboxy group,
A sulfonic acid group, a phosphonic acid group, or a C1-C4 alkyl or alkenyl group substituted with a carboxy group, a sulfonic acid group, a sulfate group, or a phosphate group.
However, R ₁₂ , R ₁₃ and R ₁₄ are not simultaneously hydrogen atoms. (2) Ultrafiltration at the time of silver halide grain formation
It is characterized by containing at least one type of silver halide emulsion produced by performing grain growth while appropriately extracting an aqueous solution containing a salt from the reaction product solution, and containing a compound represented by the following general formula (2). Silver halide photographic material.

[0014]

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[Wherein R ₃₁ , R ₃₃ , R ₃₅ and R ₃₆ each independently represent a hydrogen atom, a hydroxy group, a carboxy group,
Represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, a substituted aryloxy group, or a sugar residue.
However, R ₃₁ , R ₃₃ , R ₃₅ and R ₃₆ are not hydrogen atoms at the same time. R ₃₂ and R ₃₄ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, a substituted aryl Represents an oxy group or a sugar residue. (3) Ultrafiltration at the time of silver halide grain formation
The grain growth is carried out by appropriately extracting an aqueous solution containing a salt from the reaction solution, thereby containing at least one silver halide emulsion produced and containing a disulfide compound having a molecular weight of 500 or more. Silver photographic photosensitive material.

(4) At least one type of silver halide emulsion produced by ultrafiltration at the time of forming silver halide grains by growing the grains while appropriately extracting an aqueous solution containing a salt from the reaction solution, And a compound represented by the following general formula (4):

Formula (4): R ₅₁ -SR _{52 wherein} R ₅₁ and R ₅₂ each independently represent an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, Represents a ring group or a substituted heterocyclic group. (5) Ultrafiltration at the time of silver halide grain formation
It is characterized by containing at least one silver halide emulsion produced by grain growth while appropriately extracting an aqueous solution containing a salt from the reaction solution, and containing a compound represented by the following general formula (5). Silver halide photographic material.

Formula (5) (Me) n ₀ HAO ₃ [wherein Me represents a monovalent or divalent atom, and n ₀ represents Me
Is 2 when Me is monovalent, and 1 when Me is divalent. A represents an atom of Group 15 of the periodic table. However, nitrogen is excluded. (6) Ultrafiltration at the time of silver halide grain formation
It is characterized by containing at least one type of silver halide emulsion produced by conducting grain growth while appropriately extracting an aqueous solution containing a salt from the reaction product solution, and containing a compound represented by the following general formula (6). Silver halide photographic material.

Formula (6) R ₉₁ NH—OH wherein R ₉₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group, alkenyl group or acyl group. (7) A processing method comprising subjecting the silver halide photographic light-sensitive material according to any one of the above (1) to (6) to image processing and then photographic processing under conditions satisfying the following formula. .

Le ^0.75 × t = 40-90 (0.7 ≦ Le ≦ 4.0) [wherein, Le is the contact point between the first roller pair at the film insertion port of the automatic processor and the last roller at the film drying port. The length of the transport path to the pair (unit is m), and t represents the time required to pass through Le (unit is second). Hereinafter, the present invention will be described in more detail.

The silver halide grains produced according to the present invention may be so-called normal-crystal silver halide grains such as hexahedral, octahedral or dodecahedral grains or tabular silver halide grains. In the case of the same volume, tabular grains can adsorb more spectral sensitizing dyes on the grain surface and have the advantage of further increasing sensitivity when the same volume is used. Therefore, tabular silver halide grains are preferred.

Techniques using tabular silver halide are described in JP-A-58-111935, JP-A-58-111936, and JP-A-58-111936.
8-111937, 58-113927, 59
-99433 and the like.

The silver halide emulsion of the present invention can be produced in the process of nucleation, ripening and growth. The nucleation of tabular grains is generally performed by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding an aqueous solution of gelatin, or by a double jet method, or by adding an aqueous solution of silver salt to a gelatin solution containing an alkali halide. A single jet method for addition is used. Further, a method of adding an aqueous solution of an alkali halide to a gelatin solution containing a silver salt, if necessary, can also be used. Further, if necessary, a gelatin solution, a silver salt solution and an aqueous solution of an alkali halide are added to a mixer disclosed in JP-A-2-44335 and the mixture is immediately transferred to a reaction vessel to form nuclei of tabular grains. Can also be performed. Also, U.S. Pat.
As disclosed in Japanese Patent No. 104,786, nucleation can also be carried out by passing an aqueous solution containing an alkali halide and a protective colloid solution through a pipe and adding an aqueous solution of a silver salt thereto. Nucleation uses protective colloid as dispersion medium,
It is preferable to form a dispersion medium under the condition that pBr is 1 to 4, and particularly preferably in the range of 1 to 3.5. Protective colloids include gelatin and protective colloid polymers. As the kind of gelatin, alkali-treated gelatin is usually used, but phthalated gelatin may be used, and low molecular weight gelatin (molecular weight: 3000 to 40,000) and oxidized gelatin are preferable. The following are suitable as the protective colloid polymer. The concentration of the dispersion medium is preferably 10% by weight or less, more preferably 1% by weight or less. The temperature at the time of nucleation is preferably 5 to 60 ° C., but when producing fine tabular particles having an average particle size of 0.5 μm or less, 5 to 60 ° C.
~ 48 ° C is more preferred. The pH of the dispersion medium is desirably 8 or less, preferably 6 or less. The composition of alkali halide solution added Br ^- for I ^- content produces A
It is not more than the solid solution limit of gBrI, preferably not more than 10 mol%.

Next, in the present invention, an ultrafiltration method for appropriately extracting a solution containing a salt from a reaction solution will be described.

In FIG. 1 of the present invention, a reaction vessel 1 includes:
First, a dispersion medium 3 containing silver halide grains having undergone the grain nucleation step or the ripening step is contained together with the dispersion medium. The mechanism 2 for stirring the silver halide emulsion includes:
Although shown as a rotatable shaft with wings attached, the mechanism can be of any conventional shape. While operating the stirring mechanism, the silver salt solution for crystal growth is poured into the reaction vessel through the silver addition line 4, and simultaneously, the halide salt solution for crystal growth is poured into the reaction vessel through the halide addition line 5. The pouring nozzle can be placed at an arbitrary position, but is preferably placed at a position where it is added into the liquid from the lower part of the reaction vessel.

The volume of the substance contained in the reaction vessel is determined by taking out a part of the silver halide emulsion containing the dispersion medium as shown in the drawing through a liquid take-out line 8 (to the ultrafiltration unit 12). Can be adjusted. At this time, a dispersion medium may be appropriately added depending on the reaction conditions. The ultrafiltration device reduces the volume of the received silver halide emulsion by separating a portion of the dispersion medium as illustrated by the permeate discharge line 10 while the residual halide, called retentate, Silver halide grains are retained inside the silver emulsion. The thus-reduced silver halide emulsion, that is, the retentate, is returned to the reaction vessel by the liquid return line 9 as shown in the figure.
The ultrafiltration unit 12 has a plurality of ultrafiltration modules, and each of the ultrafiltration modules can have a structure that can use an arbitrary ultrafiltration membrane. Also,
By controlling the opening and closing of the valve, an arbitrary ultrafiltration module can be switched and selected for use.

Next, the ultrafiltration apparatus and its operation method will be described in detail.

Ultrafiltration apparatuses have been widely known as means having particular utility in the production of silver halide grains. Generally, a film is used, which allows the passage of unwanted materials and the elimination of necessary materials, such as silver halide grains. This selective separation is achieved by hydraulically pressing the solution against a synthetic semi-permeable membrane that is made to selectively pass all molecules below a certain size and leave larger molecules. Will be performed.

The ultrafiltration is carried out by circulating the dispersion in the reaction vessel while making contact with the semipermeable ultrafiltration membrane so that a pressure difference is created across the semipermeable ultrafiltration membrane. Is preferred. In general, the membrane will be permeable to only molecules of a certain size or smaller, and will contain larger molecules and pores sized to retain the silver halide grains in the dispersion. Suitable membranes are preferably about 500-30
000 or more, more preferably about 50
It can be selected from those exhibiting transmission cutoff characteristics in the molecular weight range of 0 to 50,000.

In the practice of the present invention, the cut-off molecular weight can be easily varied outside this range. It will be readily appreciated that this cut-off molecular weight should generally not be greater than the molecular weight of the protective colloid. In general, the selection of a particular permeation cut-off molecular weight depends on the size of the silver halide at the beginning of ultrafiltration and the small molecular weight material that needs to be retained in the emulsion ["retentate".
state) ”).

In the present invention, the use of a plurality of ultrafiltration membranes having different cut-off molecular weights and changing the cut-off molecular weight in the course of forming silver halide grains controls the removal of unnecessary substances from the emulsion. Is also possible. In particular, it is preferable to use an apparatus in which a plurality of ultrafiltration membranes having different cut-off molecular weights are arranged in parallel because the ultrafiltration membrane can be easily switched and used at any time during the silver halide grain formation process.

[0032] The pressure of the emulsion in contact with the ultrafiltration membrane may be varied over a wide range. Typically, for the practice of the present invention, the pressure in the reaction vessel that contacts the ultrafiltration membrane is preferably between about 100 pg and 500 pg, typically about 100 pg (7.03 kg / cm ² ). And the outlet pressure of the retentate is preferably from about 5 palg to 10 palg, typically about 10 palg
(0.703 kg / cm ² ) or less. The pressure differential across the membrane is typically about 40-60 parg (2.81
４4.22 kg / cm ² ). Of course, depending on the structure of the reaction vessel and the ultrafiltration membrane, the viscosity of the emulsion, the concentration of the retentate and the purity of the desired retentate, it is possible for a person skilled in the art to arbitrarily set the operation at a pressure outside these ranges. That is good.

The membrane used for ultrafiltration is typically an anisotropic membrane that contains very thin walls of a very fine porous structure, thereby supporting it on a thick porous structure. Useful membranes include various polymeric materials, such as polyvinyl chloride, polyvinyl carboxylate, polyvinyl formate, polyvinyl acetate,
Polyvinyl alcohol, polysulfone, polyvinyl ether, polyacrylamide, polyimide, polyester, polyfluoroalkylene (eg, polytetrafluoroethylene), and polyvinylidene fluoride, and cellulosic polymers such as cellulose and cellulose esters, such as cellulose acetate; Any material selected from cellulose butyrate and cellulose acetate butyrate can be used.

Next, the compound represented by formula (1) will be described. In the general formula (1), R ₁₁ and R ₁₅
Is preferably an alkyl group having 3 or 4 carbon atoms, a substituted alkyl group, an alkoxy group, or a substituted alkoxy, respectively. R ₁₂ , R ₁₃ and R ₁₄ are preferably a carboxy group, a sulfonic group or a phosphonic group. More preferably, two of R ₁₂ , R ₁₃ and R ₁₄ are the above groups.

The compound represented by the general formula (1) can be synthesized by a generally known method, and its preferable addition amount is 1 × 10 ^-6 to 1 × 10 ⁶ per mol of silver halide.
^-2 mol is preferably used. More preferably, 1 ×
It is 10 ^{-5 to} 5 × 10 ^-3 mol.

Hereinafter, specific examples of the compound represented by the general formula (1) of the present invention are shown, but are not limited to the following compounds.

[0037]

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[0038]

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Next, the compound represented by formula (2) will be described. In the general formula (2), R ₃₁ , R ₃₃ , R
₃₅ and R ₃₆ each independently represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, a substituted aryl axi group, Represents a residue. Provided that R ₃₁ , R ₃₃ , R ₃₅ and R ₃₆
Are not simultaneously hydrogen atoms. Among these substituents, preferred substituents are a hydroxy group, a methoxy group, a phenyloxy group, a hydroxy-substituted phenyl group, and a sugar residue, and particularly preferred are a hydroxy group and a hydroxy-substituted phenyl group. is there.

R ₃₂ and R ₃₄ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, a substituted alkoxy group. , A substituted aryloxy group or a sugar residue. Among these substituents, preferred substituents are a hydrogen atom and a hydroxy group.

The compound represented by the general formula (2) can be synthesized by a generally known method, and its preferable addition amount is 1 × 10 ^-6 to 1 × 10 ⁶ per mol of silver halide.
^-2 mol is preferably used. More preferably, 1 ×
It is 10 ^{-5 to} 5 × 10 ^-3 mol.

Specific examples of the compound represented by formula (2) of the present invention are shown below, but are not limited to the following compounds.

[0043]

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[0044]

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Next, the disulfide compound having a molecular weight of 500 or more of the present invention (hereinafter, also referred to as the disulfide compound of the present invention) will be described.

The disulfide compound of the present invention needs to have a molecular weight of 500 or more, but if the molecular weight is 500 or more, its structure and substituents are not particularly limited.
When the molecular weight is 500 or less, the effect on photographic properties is large, and it is not suitable for practical use.

The disulfide compound of the present invention can be synthesized by a generally known method. That is, it can be obtained by oxidizing a mercapto-containing compound using an enzyme or another oxidizing agent.

The following are specific examples of the disulfide compound of the present invention, but are not limited to the following compounds.

[0049]

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Next, the compound represented by formula (4) will be described. In the general formula (4), R ₅₁ and R ₅₂ are
Although each independently represents an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, or a substituted heterocyclic group, among these, an alkyl group having 1 to 6 carbon atoms, An aryl group and a heterocyclic group are preferred, and a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are more preferred. Preferred substituents are a hydroxy group, a carboxy group, a sulfo group, or an alkali metal salt thereof.

The compound represented by the general formula (4) can be synthesized by a generally known method, and its preferable addition amount is 1 × 10 ^-6 to 1 × 10 ⁶ per mol of silver halide.
^-2 mol is preferably used. More preferably, 1 ×
It is 10 ^{-5 to} 5 × 10 ^-3 mol.

Next, specific examples of the compound of the general formula (4) will be shown, but it should be understood that the present invention is not limited to these.

[0053]

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In the general formula (5), Me is monovalent or divalent.
N ₀ represents 2 when Me is monovalent, and represents 1 when Me is divalent. A represents an atom of Group 15 of the periodic table excluding nitrogen, and phosphorus is preferable. Compounds containing nitrogen are excluded because they are significantly less effective. The reason is that
It is considered that the pπ-pπ double bond can be stably formed in nitrogen, but the energy level of the 3d orbital is low in atoms higher than phosphorus, and the 3d orbital is not used in the reaction. Hereinafter, specific examples of the compound of the general formula (5) are shown, but are not limited thereto.

5-1 K ₂ HPO ₃ 5-2 Na ₂ HPO ₃ 5-3 MgHPO ₃ 5-4 K ₂ HSbO ₃ 5-5 Na ₂ HSbO ₃ 5-6 MgHSbO ₃ 5-7 K ₂ HBiO ₃ 5- 8 Na ₂ HBiO ₃ 5-9 MgHBiO ₃ The preferable addition amount of the compound represented by the general formula (5) is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide. More preferably, 1 × 10 ⁻⁵ to
5 × 10 ^-3 mol.

In the general formula (6), R ₉₁ is a hydrogen atom,
Or each substituted, represents an unsubstituted alkyl group, alkenyl group, acyl group, but represents a hydrogen atom or a substituted with 1 to 4 carbon atoms, an unsubstituted alkyl group or a substituted with 2 to 4 carbon atoms, an unsubstituted alkenyl group, An acyl group is preferable, and a substituent is preferably a group selected from a hydroxy group, a carboxy group, an amino group, a nitro group, a sulfo group, a sulfate group, and salts thereof. As R ₉₁ , an alkyl group or an alkyl group substituted with a hydroxy group is most preferred.

Specific examples of the compound represented by the general formula (6) are shown below, but the invention is not limited thereto.

[0058]

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[0059]

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The amount of the compound represented by the general formula (6) is not particularly limited, but is practically 5 × 10 ^{−5 to} 5 × 10 ⁻³ mol, preferably 1 ×, per mol of silver halide. 10 ^-4
１1 × 10 ⁻³ mol.

In the present invention, selenium compounds and / or tellurium compounds are preferably used as chemical sensitizers for silver halide grains. The selenium and tellurium compounds used include a wide variety of compounds.

The selenium compounds according to the present invention include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N, N-dimethylselenourea, triethyl-N,
N, N'-selenourea, N, N, N'-trimethyl-
N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketone (Eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophos) And selenides (eg, triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium compounds are selenides, selenoureas, selenamides, and selenoketones.

The amount of the selenium compound used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 10 ^-4 per mol of silver halide.
Use about moles.

The temperature of chemical ripening using a selenium compound is as follows:
It is preferably in the range of 40 to 90C, more preferably 45C.
Above, it is 80 degrees C or less. The emulsion pH was 4-9, pA
g is preferably in the range of 6.0 to 9.5.

Next, useful examples of tellurium compounds used in the present invention are telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea). Urea, N, N '
-Dimethyl-N'-phenyltellurourea), phosphine tellurides (for example, tributylphosphine telluride,
Tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (for example, telluroacetamide,
N, N-dimethyltellurobenzamide), telluroketones, telluroesters, isotellocyanates, and the like.

The technique for using the tellurium compound conforms to the technique for using the selenium compound. In the present invention, chemical sensitization may be performed by combining selenium sensitization and tellurium sensitization.

The silver halide composition of the silver halide photographic light-sensitive material of the present invention may be arbitrary. For example, silver chloride, silver iodochloride, silver chlorobromide, silver bromide, silver iodobromide, silver chloroiodobromide And any other silver halide may be used. When silver iodochloride is contained, the silver iodide content is preferably from 0 to 1.5 mol% as an average silver iodide content in the whole silver halide grains, and from 0 to 1.
0 mol% is more preferred.

The silver halide grains used in the present invention preferably have an average particle size of 0.15 to 5.0 μm.
It is more preferably from 0.2 to 3.0 μm, most preferably from 0.2 to 2.0 μm.

The crystal habit of the silver halide grains may be any crystal habit such as a cubic, octahedral, or twinned crystal, but tabular silver halide grains are preferred.

The tabular silver halide grains refer to grains having two opposing parallel main planes, and those which can be used in the present invention include those having the (111) plane as the main plane (1).
The (00) plane may be either a main plane or either plane.

In the tabular silver halide grains preferably used in the present invention, the ratio of the grain size to the grain thickness (hereinafter referred to as the aspect ratio) is 2 or more, preferably 2 to 1.
5 Particularly, 3 to 10 are preferable. Here, the grain size is an average projected area diameter (hereinafter, referred to as a grain size), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (of a circle having the same projected area as the silver halide grains). Diameter)
Thickness refers to the distance between two parallel main planes forming tabular silver halide grains.

When tabular silver halide grains are used in the present invention, the average grain thickness is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.60.
μm, and more preferably 0.05 to 0.50 μm.
The average particle size is preferably from 0.15 to 5.0 μm, more preferably from 0.4 to 3.0 μm, most preferably from 0.4 to 2.0 μm. The tabular silver halide grains are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = width of grain size distribution (%) Is preferably 20% or less, more preferably 15% or less.

When tabular silver halide grains are used in the present invention, they can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to form nuclei with low pCl in the presence of iodine ions under conditions that facilitate formation of the (100) plane. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution.

In the step of forming and / or growing the tabular silver halide grains, a cadmium salt,
Metal ions are added using at least one selected from a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt), and an iron salt (including a complex salt). These metal elements can also be contained on the particle surface.

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.

In the present invention, chemical sensitization with a noble metal salt such as a sulfur compound or a gold salt can also be performed, and chemical sensitization can be performed by combining these sensitization methods with the above-described chalcogen sensitization method.

Specific examples of the sulfur sensitizer applicable to the present invention include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, and rhodanine. Preferred examples include derivatives, dithiacarbamic acids, polysulfide organic compounds, and simple sulfur. In addition, as the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

As the gold sensitizer, chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, thioureas, rhodanines,
Other examples include gold complexes of 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 and the like.
It is preferably from 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol per mol. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols or other inorganic or organic solvents and adding them in the form of a solution. It may be added in the form of a dispersion obtained by emulsifying and dispersing using such a medium. Both sulfur sensitization and gold sensitization may be performed simultaneously or separately and stepwise. In the latter case, favorable results may be obtained if gold sensitization is performed after or during sulfur sensitization appropriately.

The reduction sensitization is performed by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion so that the reduction sensitization is performed during the growth of the silver halide grains of the silver halide emulsion. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof.
Other preferable reducing agents include polyamines such as hydrazine and diethylenetriamine, dimethylamineboranes, sulfites and the like.

The silver halide grains used in the present invention are:
It must be spectrally sensitized by methine dyes and the like. As the sensitizing dye used in the light-sensitive material of the present invention, cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar, hemicyanine, styryl, and hemioxonol dyes can be used. Particularly useful dyes are those belonging to cyanines, merocyanines and complex merocyanines.

As these dyes, any of the nuclei usually used can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and the like, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, Indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine or complex merocyanine includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thiooxazolidine-nucleus as ketones having a ketomethine structure.
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. Also, together with the sensitizing dye,
A dye which does not have spectral sensitization or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion layer. For example, it may contain an aminostilbene compound substituted with a nitrogen-containing heterocyclic nucleus group, a condensate of an aromatic organic acid formaldehyde, a cadmium salt, an azaindene compound, or the like.

It is more preferable to add the spectral sensitizing dye as a dispersion of solid fine particles than to add the spectral sensitizing dye as a solution of an organic solvent. In particular, it is preferable to disperse in a water system substantially free of an organic solvent and / or a surfactant, and to add in a state of a solid fine particle dispersion substantially insoluble in water. The particle size after dispersion is preferably 1 μm or less.

In the emulsion used in the silver halide photographic light-sensitive material of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening.

Compounds used in such a step include, for example, Research Disclosure (RD) N
o. 17643 (December 1978), (RD) No.
18716 (November 1979) and (RD) No. 3
Various compounds described in 08119 (December 1989) can be used.

The method of developing a silver halide photographic light-sensitive material of the present invention is processed by an automatic developing machine, and is developed, fixed, washed with water,
It is completed through a drying process.

In the present invention, the length Le of the transport path for processing is in the range of 0.7 to 4.0 (unit: m). Le
Is 0.7 or less, each processing step is shortened, and sensitivity and contrast are reduced. Further, since the number of transport rollers is reduced, transportability is deteriorated. Also, Le is 4.0.
In the case described above, the conveying speed becomes too high, and abrasion or the like is caused on the photosensitive material, which is not preferable.

The product of Le ^0.75 and t is 40 to 90. If this value is less than 40, problems such as a decrease in sensitivity and contrast or poor drying are not preferred. On the other hand, if this value exceeds 90, the situation is contrary to the recent situation where quick processing is desired. In the processing method of the present invention, both the developing solution and the fixing solution may be processed using a replenisher. The replenishment amount is not particularly limited, but the photosensitive material is divided into four.
The replenishing amount may be 6 to 90 ml per sheet, preferably 6 to 40 ml for both the developing solution and the fixing solution.

In the present invention, as a developer for a silver halide photographic light-sensitive material, for example, dihydroxybenzenes (such as hydroquinone), 3-pyrazolidones (such as 1-phenyl-3-pyrazolidone), and aminophenols (N
-Methyl-aminophenol) or reductones or the like can be used alone or in combination. As a preservative, an organic reducing agent can be used as a preservative in addition to the sulfite described in JP-A-6-138591, and the weight of a chelating agent and a hardener described in JP-A-6-138591 can be used. Sulfite adducts can be used. Japanese Patent Laid-Open No. 5-
It is also preferable to add a silver sludge inhibitor described in JP-A-289255 and JP-A-6-308680, a cyclodextrin compound described in JP-A-1-124852, and an amine compound described in U.S. Pat. No. 4,269,929.

It is necessary to use a buffer for the developer.
Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate, potassium tetraborate, sodium o-hydroxybenzoate ( Sodium salicylate), o-
Examples thereof include potassium hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, and hydrazines. , A mesoionic compound, an ionic compound, imidazoles and the like can be added as necessary.

As antifoggants, alkali metal halides such as potassium iodide and benzotriazole;
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2
Organic antifoggants such as -thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be used.

Further, the developer composition includes methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound, JP-B-47-33378,
The compound described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of a developing agent,
In addition, a stain inhibitor, an anti-sludge agent, and a layering effect promoter can also be used.

Known compounds such as fixing agents, chelating agents, pH buffers and preservatives can be used in the fixing solution. For example, those described in JP-A-4-242246 or JP-A-5-113632 can be used. it can.

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.

As an advantageous method for processing the silver halide photographic light-sensitive material of the present invention, processing is performed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank.

As the processing agent supply means, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783,
No. 97522, Japanese Utility Model Laid-Open No. 1-85732, etc., and in the case of granules or powder, Japanese Utility Model Application Laid-Open No. 62-81
964, 63-84151, JP-A 1-2923
No. 75, etc.
Nos. 59 and 63-195345, etc. can be referred to. The place where the solid processing agent is charged is in the processing tank, but it is preferably in communication with the processing section for processing the photosensitive material, where the processing liquid is flowing between the processing section and the processing section. A preferred structure is one in which there is a constant processing solution circulation amount and the dissolved components move to the processing section. Further, it is preferable that the solid processing agent is introduced into a processing liquid whose temperature is controlled.

In the processing method of the present invention, a preferable processing temperature is a developing temperature of 25 to 50 ° C. (more preferably 30 to 40 ° C.).
℃), fixing temperature 20-50 ℃ (further 30-40 ℃),
A washing temperature of 0 to 50 ° C (more preferably 15 to 40 ° C) and a drying temperature of 35 to 100 ° C (more preferably 40 to 80 ° C) are preferable.

Examples of the support used in the silver halide photographic light-sensitive material of the present invention include those described in the above-mentioned RD. A suitable support is a polyethylene terephthalate film or the like, and the surface of the support is coated. In order to improve the adhesiveness of the layer, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied.

[0103]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto.

Example 1 Preparation of Emulsion 1 (Comparative Example) A1 Ossein gelatin 75.5 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml Potassium bromide 64.7 g Water 10,800 ml B1 0.7N silver nitrate aqueous solution 470ml C1 2.0N silver nitrate aqueous solution 1,500ml D1 1.3N potassium bromide aqueous solution 410ml E1 2.0N potassium bromide aqueous solution The following silver potential control amount F1 ossein gelatin 125g water 4,000ml G1 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) Equivalent to 0.007 mol * 5.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide 6 .64 L to 7.06 mol of silver nitrate and 7.06 mol of iodine 2 L of each aqueous solution containing potassium iodide was added over 10 minutes. During the formation of fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

[Nucleation] Using a mixing stirrer shown in FIG. 1 at 55 ° C., 400 ml of the solution B1 and the entire amount of the solution D1 were added to the solution A1 by the simultaneous mixing method over 40 seconds.
Nucleation was performed.

[Aging] After the addition of the solution B1 and the solution D1, the solution F1 was added, and then the remaining amount of the solution B1 was added over 25 minutes. Further, 30 ml of a 10% aqueous ammonium nitrate solution was added, and the mixture was ripened for 10 minutes by adjusting the pH to 9.4 using a 10% aqueous potassium hydroxide solution, and the pH was adjusted to 6.0 with acetic acid.

[Growth] Solutions C1 and E1 were pAg = 7.8.
At the rate corresponding to the critical growth rate, and after adding 1,250 ml of C1, the solution C1 is added at the rate at which the addition of the solution G1 is completed simultaneously with the completion of the addition of C1.
It was added simultaneously with E1. After stirring for 5 minutes, soluble salts were desalted and removed by a sedimentation method.

In the preparation of this emulsion, the circulation of the emulsion to the liquid take-out line 8 was not performed.

The average thickness and the projected area average grain size (in terms of circle equivalent diameter) of the silver halide grains in the obtained emulsion were confirmed by an electron microscope to be 0.80 μm and 0.20 μm, respectively.
0 μm, and the variation coefficient of the projected area average particle size was 21%.

Preparation of Emulsion 2 (Invention) The process from nucleation to ripening was carried out in the same manner as for Emulsion 1.
After completion of aging, using the apparatus shown in FIG. 1, the liquid was sent from the reaction vessel to the ultrafiltration unit having a permeation cutoff characteristic of 1,500 in molecular weight by using a circulation pump in a circulation line,
A step of returning the emulsion solution to the reaction vessel while removing the permeate from the reaction vessel, a step of adding the same amount of pure water as the permeate removed to the reaction vessel, and a step of appropriately adding pure water to the reaction vessel Grain growth was carried out in the same manner as in Emulsion 1, while performing the operations in parallel. The circulation speed was set at a flow rate within a range not affecting the particle growth.

Further, the amount of the liquid in the reaction vessel at the end of the addition of the solution was adjusted so as to be the same as the amount of the liquid at the end of the emulsion 1. Thereafter, desalting was performed in the same manner as in Emulsion 1. The emulsion thus obtained is referred to as Emulsion 2.

The average thickness and the projected area average grain size (in terms of circle equivalent diameter) of the silver halide grains in the obtained emulsion were confirmed by an electron microscope to be 0.81 μm and 0.21 μm, respectively.
0 μm, and the variation coefficient of the projected area average particle size was 14%.

<Sensitization> Next, each of Emulsion 1 and Emulsion 2 was subjected to the following sensitization. The emulsion was divided into a predetermined amount and the temperature was adjusted to 55 ° C., and 0.1 mol% of silver iodide fine particles were added thereto to give 4-hydroxy-6-methyl-1,
100m of 3,3a, 7-tetrazaindene (TAI)
g, 445 mg of spectral sensitizing dye 1 and 5 parts of spectral sensitizing dye 2
mg was added as a solid particulate dispersion. Subsequently, sodium thiosulfate (15 mg), selenium sensitizer dispersion (15)
mg, ammonium thiocyanate (105 mg) and chloroauric acid (12.5 mg), and the mixture was aged for a total of 2 hours. At the end of aging, 5 mg of 1-phenyl-5-mercaptotetrazole (PMT) and 200 mg of TAI were used as stabilizers.
Was added. The amount of addition was per mole of silver.

A solid fine particle dispersion of the spectral sensitizing dye was prepared by a method according to the method described in JP-A-5-297496.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) was used.
Obtained by stirring at 00 rpm 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. 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 a dispersion blade of 40 m / sec for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3 wt% or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used for experiments.

The obtained emulsions were designated as EM-1 and EM-
And 2.

(Preparation of Emulsion EM-3-1 to 3-3) Before the start of chemical sensitization using Emulsion 2, specifically after the temperature was raised to 55 ° C., and before the addition of the sensitizing dye, the compound represented by the general formula (1) ), Specifically, (1-1), (1-3) and (1-5) were converted to 1 × 10
Sensitization was performed in the same manner as in EM-2, except that ^-3 mol / mol Ag was added. Each emulsion was EM-3-1, E
M-3-2 and EM-3-3.

The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a coating solution for a protective layer described below was prepared. Using both the coating solutions, two slide hopper type coaters were used so that the coating amount was 1.6 g / m ² per side and the amount of gelatin was 2.5 g / m ² per side.
Both sides were simultaneously coated on the support at a speed of 0 m, and dried for 2 minutes and 20 seconds to obtain a sample. As the support, glycidyl methacrylate 50 wt%, methyl acrylate 10 w
175% of a copolymer aqueous dispersion obtained by diluting the concentration of a copolymer composed of three kinds of monomers of 10% by weight and butyl methacrylate to 40% by weight was used as a subbing liquid.
A polyethylene terephthalate film base colored blue to a concentration of 0.18 for a μm X-ray film was used.

The additives used in the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

First Layer (Crossover Cut Layer) Solid Fine Particle Dispersion Dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium Dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / 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 Second layer (silver halide emulsion layer) Emulsion obtained above The following various additives were added.

Compound of general formula (1) shown in Table 1 1.0 × 10 ⁻⁵ mol / m 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) 0. _{^{mg / m 2 n-C 4}} H 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 350mg / m 2 Compound (P) 0.2g / m ² Compound (Q) 0.2g / m ² Latex (L) 0.3 g / m ² However, the 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 2,4-dichloro-6-hydroxy-1,3 2,5-Triazine sodium salt 10 mg / m ² bis-vinylsulfonyl methyl ether 36 mg / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² sodium polyacrylate 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) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3 mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ H 2 mg / m ² _{C 8 F 17 SO 2 N- (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 SO 3 Na 1mg / m 2 hardener (B) 60mg / m ² Latex (L) 0. 3 g / m ²

[0124]

Embedded image

[0125]

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[0126]

Embedded image

[0127]

Embedded image

The amount of the above-mentioned material is equivalent to one side.
The coating amount of the emulsion layer was adjusted so that the amount of silver per side was 1.3 g / m ² . Each sample obtained was evaluated as follows,
Table 1 shows the results.

<Evaluation of sensitometry (photographic performance)>
Each of the obtained samples was intensified with two intensifying screens (Konica Corporation)
Tube voltage: 60 kVp, tube current: 100 mA, X for 0.05 seconds through an aluminum wedge
The line was irradiated.

Next, a developing process described below was performed, and each obtained sample was evaluated.

The sensitivity is represented by the reciprocal of the exposure amount giving a density of fog + 1.0. The relative sensitivities are shown assuming that the sensitivity of 1 is 100. Fog indicates the optical density including the unexposed portion of the support, and Dm indicates the maximum density. Gamma was determined by measuring the slope of the logarithm of the exposure amount giving a density of 1.0 to 2.0.

The developing treatment was carried out using an automatic developing machine SRX501 (manufactured by Konica Corporation) with a developing solution and a fixing solution having the following formulations. The transport path of the SRX501 is 1.95 m.

Formulation of developer Part A (for finishing 12 L) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2,280 g Diethylenetriaminepentaacetic acid 120 g Sodium bicarbonate 132 g 5-methylbenzotriazole 1.2 g 1-phenyl-5-mercapto 0.2 g of tetrazole 340 g of hydroquinone Add water to make 5,000 ml Part B (for finishing 12 L) Glacial acetic acid 170 g Triethylene glycol 185 g 1-phenyl-2-pyrazolidone 22 g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to finish to 1.0 L Fixer formulation PartA (for finishing 18 L) Ammonium thiosulfate 6,000 g Sodium sulfite 110 g Sodium acetate.3 water 450 g sodium citrate 50 g gluconic acid 70 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part B (for finishing 18 L) Aluminum sulfate 800 g For the preparation of the developing solution, about 5 L of water and Part A and Part B simultaneously Water was added while stirring and dissolving to make 12 L, and the pH was adjusted to 10.40 with glacial acetic acid. The above-mentioned starter is added to 1 L of the development replenisher at 20 ml / L, and the pH is adjusted to 10.26 to obtain a working solution.

The fixing solution was prepared by adding Part A and P to about 5 L of water.
artB was added at the same time, and water was added while stirring and dissolving.
Finished to 8 L and adjusted pH to 4.4 using sulfuric acid and sodium hydroxide. This is used as a fixing replenisher.

The processing temperature was 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for washing, 50 ° C. for drying, and the processing time was Dry.
45 seconds for to Dry.

<Evaluation of pressure fog (roller mark)>
In this evaluation, each sample was subjected to the following treatment after X-ray exposure so that the concentration was 1.2 ± 0.5. 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 B: Small spots C: Many spots <Evaluation of processing variability (sensitivity, fog, gamma)> In the same manner as in the sensitometric evaluation. X-ray irradiated sample
The developing process was performed with the developing temperature of the automatic developing machine set at 32 ° C. and 38 ° C., and differences in sensitivity, fog and gamma from the 35 ° C. process were determined. The smaller the value is, the smaller and more stable the process fluctuation due to the development temperature is.

[0138]

[Table 1]

Example 2 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (2), specifically, (2-1), (2-2) and (2-4) was used. 1 × 10 ^-3 mol / mol Ag emulsion added ones each EM-4-1, EM-4-2 and EM-
A sample was prepared in the same manner as in Example 1 except that 4-3 was set, and evaluated in the same manner as in Example 1. Table 2 shows the obtained results.

[0140]

[Table 2]

Example 3 In place of the compound of the formula (1) of Example 1, the compound having a molecular weight of 5
00 or more disulfide compounds, specifically (3-1)
A sample was prepared in the same manner as in Example 1 except that emulsions EM-5-1 and EM-5-2 were respectively added with 1 × 10 ⁻³ mol / mole Ag and (3-4), Example 1
Was evaluated in the same way as Table 3 shows the obtained results.

[0142]

[Table 3]

Example 4 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (4), specifically, (4-1) and (4-1)
0) was added to 1 × 10 ⁻³ mol / mol Ag to prepare emulsions EM-6-1 and EM-6-2, respectively, except that samples were prepared in the same manner as in Example 1. It was evaluated similarly. Table 4 shows the obtained results.

[0144]

[Table 4]

Example 5 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (5), specifically, (5-2) and (5-3)
Was prepared in the same manner as in Example 1 except that emulsions EM-7-1 and EM-7-2 were respectively added with 1 × 10 ⁻³ mol / mol Ag. evaluated. Table 5 shows the obtained results.

[0146]

[Table 5]

Example 6 Instead of the compound of the general formula (1) of Example 1, the compound of the general formula (6), specifically, (6-2), (6-3) and (6-10) Emulsions EM-8-1, EM-8-2, and EM to which 1 × 10 ⁻³ mol / mol Ag was added, respectively
A sample was prepared in the same manner as in Example 1 except that -8-3 was set, and evaluated in the same manner as in Example 1. Table 6 shows the obtained results.
Shown in

[0148]

[Table 6]

Tables 1 to 6 show that the sample of the present invention is a silver halide photographic material having high sensitivity, low fog, improved pressure resistance, and low processing variability.

[0150]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity, low fog, good pressure resistance, and little processing fluctuation, and a processing method thereof can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a silver halide emulsion manufacturing apparatus applicable to the manufacturing equipment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction container 2 Stirring mechanism 3 Dispersion medium 4 Silver addition line 5 Halide addition line 6 Dispersion medium addition line 7 Addition line 8 Liquid take-out line 9 Liquid return line 10 Permeate discharge line 11 Permeate return line 12 Ultrafiltration unit 13 Circulation Pump 14 Flow meter 15, 16, 17 Pressure gauge 18 Pressure adjusting valve 19 Flow adjusting valve 20 Silver addition valve 21 Halide addition valve 22 Liquid extraction valve 23, 24, 25 Valve 26 Ultrafiltration permeate 27 Permeate receiver 28 scales

Claims (7)

[Claims] Claims: 1. At least one silver halide emulsion produced by ultrafiltration at the time of silver halide grain formation by growing grains while appropriately extracting an aqueous solution containing a salt from a reaction solution, and A silver halide photographic material comprising a compound represented by the following general formula (1). Embedded image [Wherein, R ₁₁ and R ₁₅ each independently have 1 to 5 carbon atoms.
Represents an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, and a cyano group. R ₁₂ , R ₁₃ and R ₁₄ are
Each independently having 1 to 4 carbon atoms substituted with a hydrogen atom, a carboxy group, a sulfonic acid group, a phosphonic acid group, or a carboxy group, a sulfonic acid group, a sulfate group, or a phosphate group;
Represents an alkyl group or an alkenyl group. However, R ₁₂ ,
R ₁₃ and R ₁₄ are not hydrogen atoms at the same time. ] 2. A silver halide emulsion containing at least one silver halide emulsion produced by ultrafiltration at the time of silver halide grain formation while growing a grain while appropriately extracting an aqueous solution containing a salt from a reaction solution; and A silver halide photographic material comprising a compound represented by the following general formula (2). Embedded image [Wherein, R ₃₁ , R ₃₃ , R ₃₅ and R ₃₆ each independently represent a hydrogen atom, a hydroxy group, a carboxy group, an alkyl group,
Represents an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, a substituted aryloxy group, or a sugar residue. However,
R ₃₁ , R ₃₃ , R ₃₅ and R ₃₆ are not hydrogen atoms at the same time. R ₃₂ and R ₃₄ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, a substituted aryl Represents an oxy group or a sugar residue. ] 3. The silver halide emulsion contains at least one type of silver halide emulsion produced by ultrafiltration at the time of silver halide grain formation while conducting grain growth while appropriately extracting an aqueous solution containing a salt from a reaction solution, and Molecular weight 50
A silver halide photographic material comprising 0 or more disulfide compounds. 4. A silver halide emulsion containing at least one silver halide emulsion produced by ultrafiltration at the time of silver halide grain formation while growing the grains while appropriately extracting an aqueous solution containing a salt from the reaction solution, and A silver halide photographic light-sensitive material comprising a compound represented by the following general formula (4). Formula (4) R ₅₁ -SR _{52 wherein} R ₅₁ and R ₅₂ each independently represent an alkyl group having 1 to 8 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, Represents a substituted heterocyclic group. ] 5. A silver halide emulsion containing at least one silver halide emulsion produced by ultrafiltration at the time of silver halide grain formation while growing the grains while appropriately extracting an aqueous solution containing a salt from the reaction solution, and A silver halide photographic light-sensitive material comprising a compound represented by the following general formula (5). Formula (5) (Me) n ₀ HAO ₃ [wherein Me represents a monovalent or divalent atom, and n ₀ is Me
Is 2 when Me is monovalent, and 1 when Me is divalent. A represents an atom of Group 15 of the periodic table. However, nitrogen is excluded. ] 6. At least one type of silver halide emulsion produced by ultrafiltration at the time of silver halide grain formation by performing grain growth while appropriately extracting an aqueous solution containing a salt from a reaction solution, and A silver halide photographic material comprising a compound represented by the following general formula (6). Formula (6): R ₉₁ NH—OH wherein R ₉₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group, alkenyl group, or acyl group. ] 7. A processing method, comprising subjecting the silver halide photographic material according to claim 1 to imagewise exposure and then photographic processing under conditions satisfying the following formula. Le ^0.75 × t = 40 to 90 (0.7 ≦ Le ≦ 4.0) [wherein, Le is the distance from the contact point of the first roller pair at the film insertion port of the automatic developing machine to the last roller pair at the film drying port]. The length of the transport path (unit is m), and t represents the time (unit: seconds) required to pass through Le. ]