JP2003315950A - Photosensitive silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity and high density (high Dmax) in rapid processing and ensuring little stain after processing. <P>SOLUTION: A photosensitive silver halide emulsion is provided in which silver halide grains have an average aspect ratio of ≥8 and which contains compounds of formulae (I), (II) and/or (III) added in or after a desalting process when the grains are prepared. In the formula (I), R<SB>1</SB>is alkyl or the like; R<SB>2</SB>-R<SB>6</SB>are each H or a substituent, provided that one of R<SB>2</SB>-R<SB>6</SB>is aryl; and X<SP>-</SP>is a counter anion. In the formulae II, III, A<SB>1</SB>-A<SB>4</SB>are each a substituent for forming an N-containing heterocycle; B is a divalent group; m is 0 or 1; R<SB>7</SB>and R<SB>8</SB>are each alkyl; X is an anion; and n is 0, 1 or 2. The silver halide photographic sensitive material contains the emulsion. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a silver halide photographic light-sensitive emulsion, and particularly to a medical X-ray silver halide for high-speed processing which has high sensitivity and less residual color. The present invention relates to a photographic light-sensitive material and a silver halide photographic light-sensitive emulsion.

[0002]

2. Description of the Related Art Tabular silver halide grains (hereinafter also referred to as "tabular grains") have the following advantages as photographic characteristics. 1) Ratio of surface area to volume (hereinafter referred to as specific surface area)
Is large and a large amount of sensitizing dye can be adsorbed on the surface, so that the color sensitizing sensitivity is relatively high with respect to the intrinsic sensitivity. 2) When an emulsion containing tabular grains is coated and dried, the grains are arranged parallel to the surface of the support, so that the thickness of the coating layer can be reduced and the photographic light-sensitive material has good sharpness. 3) In a radiographic system, addition of a sensitizing dye to tabular grains can significantly reduce silver halide crossover light and prevent deterioration of image quality. 4) An image with high resolution can be obtained with little light scattering. 5) The covering power (optical density of developed silver per unit amount of silver) is increased, the required amount of silver can be reduced, which is advantageous for rapid processing and reduction of coating chemical amount.

Since the tabular grains having a larger aspect ratio have a larger specific surface area, the advantages of the tabular grains described above can be greatly utilized. That is, by adsorbing a large amount of sensitizing dye onto a larger surface area, the amount of light absorbed per grain can be increased, and high sensitivity can be obtained. Therefore, many studies have been made on methods for preparing thinner tabular grains. Tokkyo 5-12
Japanese Patent No. 696 discloses a method of preparing thin tabular grains by using, as a dispersion medium, gelatin in which methionine groups in gelatin are oxidized to be inactivated. JP-A-8-8288
Japanese Patent Publication No. 3 discloses a method of preparing thin tabular grains by using gelatin in which amino groups and methionine groups are deactivated as a dispersion medium. In addition, JP-A-10-148897
The publication discloses a method of preparing thin tabular grains by chemically modifying amino groups in gelatin and using gelatin having at least two carboxyl groups introduced therein as a dispersion medium. Further, Japanese Patent Laid-Open No. 2001-147500 discloses a method for preparing ultrathin tabular emulsion grains having a (111) main plane using a pyridinium compound or a bispyridinium compound.

By the way, during processing of color photographic materials, silver halide is removed from the light-sensitive material. In black-and-white photographic materials, unexposed silver halide is removed. In either case, it is desirable that the sensitizing dye be removed as well. Sensitizing dyes that are not removed tend to cause residual color and adversely affect the image recorded on the photographic material. The residual color problem is exacerbated by the increased use of tabular grain emulsions. The tabular grain emulsion has a large surface area per 1 mol of silver and a large amount of sensitizing dye is added, so that the residual color is relatively large. Further, when used for rapid processing, the problem of residual color is particularly likely to become apparent.

By adding a sensitizing dye before chemically sensitizing the emulsion grains, the chemical sensitization can be controlled and the sensitivity / fog ratio can be improved. However, by increasing the aspect ratio of the particles, the surface area of the particles increases and a large amount of the required sensitizing dye is required,
There was also a problem that the residual color deteriorates. Note that the above-mentioned Japanese Patent Laid-Open No. 2001-147550 also discloses a technique using the same pyridinium compound as the present invention,
The patent incorporates a pyridinium compound during grain formation,
It is a technique for preparing ultrathin tabular grains, which is essentially different from the technique of the present invention used for controlling photographic performance after grain formation.

[0006]

In view of the above problems of the prior art, the problems to be solved by the present invention are high sensitivity, high density (high Dmax) even in rapid processing, and residual color after processing. A small amount of a silver halide photographic light-sensitive material and a light-sensitive silver halide emulsion are provided.

[0007]

The above objects have been achieved by the following means. (1) The average aspect ratio of silver halide emulsion grains is 8
A photosensitive silver halide emulsion characterized in that the compounds of the following general formulas (I), (II) and / or (III) are added after the desalting step at the time of preparing the emulsion grains.

[0008]

[Chemical 3]

(Wherein R ₁ is an alkyl group, an alkenyl group,
Represents an aralkyl group, and R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a substituent. R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ , and R ₅ and R ₆ may be condensed. However, at least one of R ₂ , R ₃ , R ₄ , R _5, and R ₆ represents an aryl group. X ^- represents a counter anion. )

[0010]

[Chemical 4]

(In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent a non-metal atom for completing a nitrogen-containing heterocycle,
Each may be the same or different. B represents a divalent linking group. m represents 0 or 1. R ₇ and R ₈ each represent an alkyl group. X ^- represents an anion. n is 0,
Represents 1 or 2, and n is 0 or 1 in the case of an inner salt. (2) The average equivalent circle diameter of silver halide emulsion grains is 1.0
The photosensitive silver halide emulsion as described in (1) above, which has a thickness of not less than μm and an average thickness of not more than 0.15 μm. (3) A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support,
The average aspect ratio of the silver halide emulsion grains in the light-sensitive silver halide emulsion layer is 8 or more, and after the desalting step at the time of preparing the emulsion grains, the general formula (I), (II) and / or (III ) A silver halide photographic light-sensitive material, characterized in that the compound (1) is added. (4) The average equivalent circle diameter of silver halide emulsion grains is 1.0
The silver halide photographic light-sensitive material as described in (3) above, which has a thickness of not less than μm and an average thickness of not more than 0.15 μm.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The compound represented by formula (I), (II) or (III) used in the present invention will be described in detail. In the general formula (I), R ₁ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group). Group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group),
An alkenyl group having 2 to 20 carbon atoms (for example, an allyl group, 2
-Butenyl group, 3-pentenyl group) and aralkyl group having 7 to 20 carbon atoms (eg, benzyl group, phenethyl group) are preferable. Each group represented by R ₁ may be substituted. Examples of the substituent include the substitutable groups represented by R _{2 to} R ₆ below.

R ₂ , R ₃ , R ₄ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom or a group capable of substituting it. Examples of the substitutable group include the following. Halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group (for example, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group, etc.), alkoxy group, aryloxy group, amino group , Acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, acyl group, acyloxy group, phosphoramide group, alkylthio group, arylthio group, cyano group , A sulfo group, a carboxy group, a hydroxy group, a phosphono group, a nitro group, a sulfino group, an ammonio group (for example, a trimethylammonio group and the like), a phosphonio group, a hydrazino group and the like. These groups may be further substituted. R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ , R
₅ and R ₆ may be condensed, and examples of the ring formed include a quinoline ring, an isoquinoline ring, and an acridine ring. X ^- represents a counter anion. Examples of the counter anion include halogen ions (chlorine ion, bromine ion), nitrate ion, sulfate ion, p-toluenesulfonate ion, trifluoromethanesulfonate ion and the like. In the general formula (I), it is preferable that R ₁ represents an aralkyl group and at least one of R ₂ , R ₃ , R ₄ , R ₅ and R ₆ represents an aryl group, and among them, R ₄ represents an aryl group. It is more preferable that X ⁻ represents a halogen ion. Examples of these compounds are disclosed in JP-A-8-22711.
However, the present invention is not limited to these. Particularly preferred are the following compounds.

[0014]

[Chemical 5]

Next, the compounds of the general formulas (II) and (III) used in the present invention will be explained in detail. In the general formulas (II) and (III), A ₁ , A ₂ , A ₃ and A ₄ each represent a non-metal atom for completing the nitrogen-containing heterocycle. Examples of the non-metal element include oxygen atom, nitrogen atom and sulfur atom. The heterocycle containing and including A ₁ , A ₂ , A ₃ and A ₄ may have a substituent, and each may be the same or different. Also,
The rings may be condensed with each other. As the substituent, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an aryloxy group, an amide group, Sulfamoyl group, carbamoyl group, ureido group,
It represents an amino group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group and an arylthio group.
Preferred examples of the heterocycle containing and containing A ₁ , A ₂ , A ₃ and A ₄ include a 5- to 6-membered ring (for example, a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring,
Pyrazine ring, pyrimidine ring and the like). Of these, a pyridine ring is preferable. B represents a divalent linking group. The divalent linking group, an alkylene group, an arylene group, an alkenylene _{group, -SO 2 -, - SO -} , - O
-, - S -, - CO -, - N (R 9) - (R 9 is an alkyl group, an aryl group or a hydrogen atom,.) Represents what is configured alone or in combination. Preferred examples of B include an alkylene group and an alkenylene group. m represents 0 or 1. R ₇ and R ₈ each represent an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms. R ₇ and R ₈ may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and examples of the substituent include the examples given as the substituents of A ₁ , A ₂ , A ₃ and A ₄ . Each of R ₇ and R ₈ is preferably an alkyl group having 4 to 10 carbon atoms, and more preferably an alkyl group substituted with a substituted or unsubstituted aryl group. X ^- represents an anion. Examples thereof include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, and oxalate. n represents 0 or 1, and in the case of an intramolecular salt, n is 0 or 1. Specific examples of the compound represented by the general formula (II) or the general formula (III) are disclosed in Japanese Patent Laid-Open No. Hei 2
No. 32 (Compound Examples 1 to 42), the present invention is not limited to these compounds. Particularly preferred are the following compounds.

[0016]

[Chemical 6]

The amount of the compound represented by formula (I), (II) or (III) used in the present invention is 1 × 10 ^-4 to 1 × 10 ^-1 mol per mol of silver halide. And particularly preferably 3 × 10 ^{−4 to} 3 × 10 ⁻² mol.

General formula (I), (II) or (II
The compound of I) may be added at any time after the desalting step. Specifically, there are a method of adding in the silver halide emulsion desalting step, a method of adding just before the silver halide emulsion chemical sensitizing step, a method of adding during the silver halide emulsion chemical sensitizing step, etc. Gold sensitizer,
It is preferable to add before the chalcogen sensitizer, that is, before the chemical sensitization with these compounds.

Next, the silver halide emulsion grains in the present invention will be described in detail. The silver halide emulsion grains of the present invention include silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiodobromide,
It may have any silver halide composition such as silver bromide and silver iodobromide. Silver iodobromide is preferable in that high sensitivity can be obtained, and silver chloride and silver chlorobromide are preferably used in terms of good fixability.

However, the silver iodide content is preferably 1 mol% or less, more preferably 0 mol% or more and 0.45 mol% or less, based on the amount of silver contained in the silver halide emulsion grains.

In the photosensitive silver halide emulsion of the present invention, the silver halide emulsion grains have an average aspect ratio of 8 or more. The aspect ratio of a silver halide emulsion grain is defined as the value obtained by dividing the equivalent circle diameter of the projected area of one grain by the thickness of the grain. The aspect ratio is preferably 8 or more and 30 or less, and more preferably 8 or more and 25 or less. The aspect ratio within the above range is most preferable in that the developed silver color tone is good and the optical density per unit developed silver amount is high.

The average circle-equivalent diameter and the average thickness of the projected areas of silver halide emulsion grains are calculated as the average value of all silver halide emulsion grains. In the present invention, the average equivalent circle diameter is preferably 1.0 μm or more, and more preferably 1.0 μm or more and 3.0 μm or less. The average thickness is preferably 0.15 μm or less, more preferably 0.03 μm or more and 0.1 μm or less.

In the present invention, the silver halide emulsion grains may be double twin grains having two parallel twin planes. Further, it may be a tabular grain having a {111} plane as a main plane or a tabular grain having a {100} plane as a main plane.

In the present invention, the silver halide emulsion grains are so-called tabular grains having an average aspect ratio of 8 or more. In the silver halide emulsion, isotropic grains such as cubes, octahedra and tetradecahedrons are used. One that has grown physically or one that has a multifaceted crystal form such as a sphere may be used in combination.

The proportion of tabular silver halide grains having an average aspect ratio of 8 or more is preferably such that the sum of the projected areas thereof is 50% or more and 100% or less with respect to the sum of the projected areas of all grains, and more preferably 70% or more and 100% or less, most preferably 90% or more and 100% or less.

The method for producing tabular silver halide grains is as follows:
The methods known in the art can be appropriately combined and used.

Further, a tabular grain having parallel twin planes and having a {111} plane as a main plane is disclosed in JP-A-58-12792.
7, JP-A-58-113927, JP-A-58-11
It can be easily prepared by referring to the method described in No. 3928.

Further, a relatively low pBr of pBr 1.3 or less
It can also be obtained by forming a seed crystal in which tabular grains are present in an amount of 40% or more by mass in an atmosphere of a certain value, and growing a seed crystal while simultaneously adding silver and a halogen solution while maintaining a similar pBr value. .

In this grain growth process, it is desirable to add silver and halogen solutions so that new crystal nuclei are not generated.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the kind and amount of the solvent, the addition rate of the silver salt used during grain growth, and the halide.

Further, in the present invention, of the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains.

The details of the structure and manufacturing method of the monodisperse hexagonal tabular grains are as described in JP-A-63-151618.

The silver halide emulsion preferably used in the present invention may have a uniform crystal structure, but may have a different halogen composition inside and outside, or may have a layered structure. Further, it is preferable that reduction sensitized silver nuclei are contained during grain formation.

In the present invention, British Patent No. 635841
So-called halogen conversion type (conversion type) particles as described in U.S. Pat. No. 3,622,318 can be used particularly effectively. The amount of halogen conversion is preferably 0.05 mol% to 0.45 mol% and more preferably 0.1 mol% to 0.3 mol% with respect to the amount of silver.

In the silver iodobromide emulsion, grains having a structure having a high iodine layer inside and / or on the surface thereof are particularly preferable.

Further, by converting the surface of the tabular silver halide grains preferred in the present invention into a high iodine type, a silver halide emulsion having higher sensitivity can be obtained.

When the halogen conversion is carried out by the above method, the method in which a silver halide solvent is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates and 4-substituted thioureas. Among them, thioether compounds and thiocyanates are particularly effective, and it is preferable to use thiocyanate in an amount of 0.5 g to 5 g and thioether in an amount of 0.2 g to 3 g per mol of silver halide.

As a method for growing the silver halide grains of the present invention, any method known so far can be used. That is, the silver salt aqueous solution and the halogen salt aqueous solution are added to the reaction vessel under efficient stirring. As a specific method, P. Glafkides, Chem
ie et Phisique Photograph
issue (Paul Montel, 1967)
Year), G. F. Duffin, Photograph
ic Emulsion Chemistry (Th
e Focal Press, 1966), V.I.
L. Zelikmanet al, Making a
nd Coating Photographic E
mulsion (published by The Focal Press,
1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. Good.

As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. Further, British Patent No. 1535016, Japanese Patent Publication Nos. 48-36890 and 52-1636.
No. 4, etc., a method of changing the addition rate of silver nitrate or an alkali halide aqueous solution according to the particle growth rate, US Pat. No. 4,242,445,
It is also preferable to use the method of changing the concentration of the aqueous solution as described in JP-A-55-158124 and the like to rapidly grow in a range not exceeding the critical supersaturation degree.

The tabular grains are preferably grown by physical ripening (fine grains are dissolved and substrate grains are grown) in the presence of fine silver halide grains for crystal growth.

In the method of adding a fine grain emulsion, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.1 μm or less.
Add an AgX fine grain emulsion having a diameter of 06 to 0.006 μm,
Tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or continuously. The fine grain emulsion can be continuously prepared by supplying the AgNO ₃ solution and the X ^- salt solution in a mixer provided in the vicinity of the reaction vessel and immediately adding it to the reaction vessel immediately, or by adding it in advance in another vessel. It is also possible to add it continuously or continuously after the preparation in batch. Such a fine grain emulsion can be added in the form of a liquid or a dry powder. It is also possible to mix the dry powder with water immediately before addition to liquefy it and add it. The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes.
When the disappearance time becomes long, ripening occurs between the fine particles and the particle size becomes large, which is not preferable. Therefore, it is preferable not to add the entire amount at once. It is preferable that such fine particles are substantially free of multi-twin grains. Here, the multi-twin grain means a grain having two or more twin planes per grain. The term "substantially free" means that the number ratio of multiple twinned grains is 5% or less, preferably 1% or less, more preferably 0.1% or less. Further, it is preferable that substantially no single twin crystal grains are contained. Furthermore, it is preferable that the screw dislocation is not substantially contained. Here, the term "substantially free" is in accordance with the above-mentioned rules.

In the step of nucleating tabular silver halide grains, gelatin having a low methionine content described in US Pat. Nos. 4,713,320 and 4,942,120 is used. 4,914,014
Nucleation with high pBr described in Japanese Patent Application Laid-Open No. 2-2
Performing nucleation in a short time as described in No. 22940 is extremely effective in the step of nucleating particles used in the present invention. Particularly, the methionine content is preferably 0 to 50 μm.
Mol / g, more preferably 0 to 40 μmol / g gelatin can be preferably used. When such gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. In the present invention, it is particularly preferable to add the silver nitrate aqueous solution, the halogen aqueous solution and the low molecular weight oxidation-treated gelatin within 1 minute under stirring in the presence of the low-molecular weight oxidation-treated gelatin at a temperature of 20 ° C. to 40 ° C. At this time, the pBr of the system is 2
The above is preferable and the pH is preferably 7 or less. The concentration of the aqueous silver nitrate solution is preferably 0.6 mol / liter or less.
Gelatin having a molecular weight smaller than that of a usual one is preferable, and 10,000 to 50,000 is particularly preferable. 90 amino groups for phthalation, succination, or trimellitization
% Or more modified gelatin and / or oxidatively processed gelatin having a reduced methionine content is particularly preferably used.

Further, the aging step can be carried out in the presence of a low-concentration base described in US Pat. No. 5,254,453 and at a high pH described in US Pat. No. 5,013,641. Is. Also, U.S. Pat. Nos. 5,147,771, 5,147,772,
No. 5,147,773, No. 5,171,659
No. 5,210,013 and No. 5,25
It is possible to add the polyalkylene oxide compound described in No. 2,453 in the aging step or the subsequent growth step. In the present invention, the aging step is preferably 60 ° C.
It is performed at a temperature of 80 ° C or lower. It is preferable to reduce pBr to 2 or less immediately after nucleation or during ripening. Further, additional gelatin is preferably added immediately after nucleation to the end of ripening. Particularly preferred gelatin is one in which 95% or more of the amino groups are modified to be succinic or trimellitic.

The pH during growth by adding fine particles is 2.0.
The above is required, but 6 or more and 10 or less are preferable. The pH is more preferably 6 or more and 9 or less.

Although pCl needs to be 1.0 or more, 1.6 or more is preferable. More preferably, it is 1.8 or more and 3.0 or less.

The tabular grains of the present invention are preferably silver halide grains having dislocation lines.

The dislocation lines of tabular grains can be calculated according to the method described in J. F.
Hamilton, Photo. Sci. Eng. , 1
1,57 (1967) and T.I. Shiozawa, J .;
Soc. Photo. Sci. Japan, 35, 213
It can be observed by a direct method using a transmission electron microscope at low temperature described in (1972). In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed so as to prevent damage (printout, etc.) due to electron beams. Observation is carried out by the transmission method in the cooled state. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μ). From the photograph of the grains obtained by such a method, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt, etc. are allowed to coexist. Good.

As the chemical sensitization in the present invention, gold sensitization is used in combination with chalcogen sensitization such as sulfur sensitization, selenium sensitization and tellurium sensitization.

In sulfur sensitization, an unstable sulfur compound is used, and P. Grafkides, Chimie et
Physique Photographique
(Paul Momtel, 1987, 5th
Edition), Research Disclosure magazine, 3
Unstable sulfur compounds described in Vol. 07, 307105 and the like can be used. Specifically, thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-N′-).
(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (for example,
Thioacetamide), rhodanines (for example, diethyl rhodanine, 5-benzylidene-N-ethyl-rhodamine), phosphine sulfides (for example, trimethylphosphine sulfide), thiohydantoins, 4-
Known sulfur compounds and activities such as oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg, dimorpholine disulfide, cystine, lenthionine), mercapto compounds (eg, cystine), polythionates, elemental sulfur, etc. Gelatin etc. can also be used.

In the sensitization of selenium, an unstable selenium compound is used, and Japanese Patent Publication Nos. 43-13489 and 44-157 are used.
48, JP-A-4-25832 and 4-109240.
JP-A-4-271341, JP-A-5-4032
Unstable selenium compounds described in No. 4 can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenamides (eg, selenoacetamide, N, N-diethylphenyl selenamide), phosphine selenides (for example, triphenylphosphine selenide, pentafluorophenyltriphenylphosphine selenide), selenophosphates (for example, tri-p-tolyl selenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids,
Selenoesters and diacyl selenides may be used. Furthermore, Japanese Patent Publications Nos. 46-4553 and 52-3.
The non-unstable selenium compounds described in Japanese Patent No. 4492, such as selenious acid, potassium selenocyanide, selenazoles, and selenides, can also be used.

In the tellurium sensitization, an unstable tellurium compound is used, and Canadian Patent 800958 and British Patent Nos. 1 and 2 are used.
95,462 and 1,396,696 each specification,
Unstable tellurium compounds described in JP-A-4-204640, 4-271341, 4-333043, and 5-303157 can be used. Specifically, telluroureas (eg, tetramethyl tellurourea, N, N′-dimethylethylene tellurourea,
N, N′-diphenylethylene tellurourea), phosphine tellurides (eg, butyl-diisopropylphosphine telluride, tributylphosphine telluride,
Tributoxy phosphine telluride, ethoxy-diphenyl phosphine telluride), diacyl (di) tellurides (for example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl) -N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), isotellocyanates, telluroamides, tellurohydrazides, telluroesters (for example, butylhexylteluro) Ester), telluroketones (for example,
(Telloacetophenone), colloidal tellurium, (di) tellurides, and other tellurium compounds (potassium telluride, telluropentathionate sodium salt) and the like may be used.

Regarding the gold sensitization, the above-mentioned P. Grafk
by des Chimes et Physique P
photographique (Paul Momtel
(Published in 1987, 5th edition), Research Di
Gold salts described in, for example, Sclosure Vol. 307, No. 307105 can be used. In particular,
In addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide, US Pat. Nos. 2,642,361 and 5,049,484
No. 5,049,485 and the like can also be used. Further, a noble metal salt such as platinum, palladium or iridium may be added.

The amount of the chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, the chemical sensitization conditions and the like, but it is 10 ^-8 to 10 ^-10 mol per mol of silver halide.
^-2 mol, preferably about 10 ^{-7 to} 5 × 10 ^-3 mol is used.

The amount of the gold sensitizer and the noble metal sensitizer used in the present invention is 10 ^-7 to 1 per mol of silver halide.
Use about 0 ^-2 mol. The conditions of the chemical sensitization in the present invention are not particularly limited, but pAg is preferably 6 to 11, more preferably 7 to 10, and pH is 4 to 4.
10 is preferable, and the temperature is preferably 40 to 95 ° C, more preferably 45 to 85 ° C.

Regarding reduction sensitization, the above-mentioned P. Graf
kids, Chimie et Physique
Photographique (Paul Momte
Publishing Company, 1987, 5th edition), Research D
Known reducing compounds described in isclosure, vol. 307, 307105, etc. can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (eg, dimethylamineborane), hydrazine compound (eg, hydrazine, p-tolylhydrazine), polyamine compound (eg, diethylenetriamine, triethylene). Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas and the like may be used. Further, reduction sensitization may be carried out in an atmosphere of high pH or silver ion excess (so-called silver ripening).

In the silver halide emulsion of the present invention, the grain surface or a part thereof may be halogen-converted in the chemical sensitization step. As a method of applying halogen conversion,
Water-soluble bromide salts such as potassium bromide and sodium bromide, water-soluble iodide salts such as potassium iodide and the like can be used alone or in combination, and they are added as solids or as an aqueous solution or gelatin dispersion. can do. Further, it is also preferable to add silver bromide, silver iodobromide, and silver halide fine grains of silver iodide, and these can be used alone or in combination. When added in the form of fine particles, the average equivalent spherical diameter of the fine particles is preferably 0.1 μm or less, more preferably 0.05 μm or less. Further, fine particles can be continuously adjusted by supplying an aqueous solution of silver nitrate and an aqueous solution of an alkali halide having an arbitrary composition with a mixer provided in the vicinity of the reaction vessel, and can be immediately added to the reaction vessel, or can be previously added to another vessel. It is also possible to add it after adjusting it in a batch manner. If necessary, the fine silver halide grains may contain ions or compounds of heavy metals such as iridium, rhodium and platinum.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added during grain formation, after grain formation, or before chemical sensitization, when grain surface modification or as a chemical sensitizer is used. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, LaCr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates, hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example CdB
r ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , P
b (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (N
H ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃
RhCl ₆ , K ₄ Ru (CN) _{6 and the} like can be mentioned. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but two or three types
You may use it in combination of 2 or more types.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present.

It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,4.
11,914, 3,554,757, JP-A-58.
No. 126526 and the aforementioned Daffin, "Photographic Emulsion Chemistry", pages 138-143.

During the process of producing the emulsion of the present invention, acid for silver is used.
It is preferable to use an agent. What is an oxidizing agent for silver?
A compound that acts on metallic silver to convert it to silver ions
It means compound. Especially the formation process and formation of silver halide grains
The extremely small silver particles produced as a by-product in the academic sensitization process
Compounds that convert to silver ions are effective. Generated here
The silver ions used are silver halide, silver sulfide, silver selenide, etc.
May form a sparingly soluble silver salt in water,
An easily soluble silver salt may be formed in water. Oxidizer for silver
May be an inorganic substance or an organic substance. Inorganic
Oxidants include ozone, hydrogen peroxide and its adducts
(For example, NaBO₂・ H₂O₂・ 3H₂O, 2NaCO₃
・ 3H₂O₂, Na_FourP₂O₇・ 2H₂O₂2Na₂SO_Four・
H₂O₂・ 2H ₂O), peroxyacid salts (eg K₂S
₂O₈, K₂C₂O₆, K₂P₂O₈), Peroxy complex compounds
(For example, K₂[Ti (O₂) C₂O_Four] ・ 3H₂O, 4K₂
SO_Four・ Ti (O₂) OH / SO_Four・ 2H₂O, Na₃[V
O (O₂) (C₂H_Four)₂・ 6H₂O], permanganate
(For example, KMnO_Four), Chromates (eg, K₂Cr
₂O₇) Such as oxygenates, halogen sources such as iodine and bromine
Element, perhalogenate (eg potassium periodate) High atom
Valuate metal salts (eg, potassium hexacyanoferrate)
) And thiosulfonate.

As the organic oxidizing agent, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T). , Chloramine B). It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination.

The silver halide photographic light-sensitive material of the present invention is preferably spectrally sensitized. Examples of the spectral sensitizing dye that can be used for spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
Examples thereof include holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful spectral sensitizing dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
As the basic heterocyclic nucleus, any of the nuclei normally used for cyanine dyes can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus,
Selenazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, tellurazole nuclei; nuclei in which alicyclic hydrocarbon rings are condensed to these nuclei; and aromatics to these nuclei Nuclei in which a group hydrocarbon ring is condensed, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, benzothiazole nucleus, natophthiazole nucleus, benzoselenazole nucleus A nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzoterazole nucleus, etc. can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

For the merocyanine dye or the composite merocyanine dye, as the nucleus having a ketomethylene structure, any nucleus generally used for merocyanine dyes can be applied. Particularly useful nuclei include pyrazolin-5-one nuclei, thiohydantoin nuclei, and 2-thiooxazolidine-2,4-
Applying 5-membered and 6-membered heterocyclic nuclei such as dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus and 2-thioselenazolidine-2,4-dione nucleus You can

As the spectral sensitizing dye used in the present invention,
It is preferable to use a sensitizing dye represented by the following general formula (IV).

[0066]

[Chemical 7]

The general formula (IV) will be described in detail below.
In the formula, R ₄₁ and R _{42 each} represent a substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 18 carbon atoms, more preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, a dodecyl group, and an octadecyl group. As the substituted alkyl group, for example, an aralkyl group (for example, benzyl, 2-phenylethyl, etc.), a hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl, etc.), a carboxyalkyl group (for example, 2-carboxyethyl, 3-). Carboxypropyl, carboxyethyl, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group, etc.), alkoxyalkyl group (eg, 2-methoxyethyl group, 2- (2-methoxyethoxy) ethyl group, etc.), sulfo Alkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-
Sulfobutyl group, 2- (3-sulfopropoxy) ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group, etc.), sulfatoalkyl group (for example, 3-sulfatopropyl group, 4- A sulfatobutyl group), a heterocyclic-substituted alkyl group (for example, 2-pyrrolidin-2-one-1-yl) ethyl group,
Tetrahydrofurfuryl group, 2-morpholinoethyl group, etc.), 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, allyl group, etc.), aryl group (for example, phenyl group, 2-naphthyl group, etc.) A substituted aryl group (eg, 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group, etc.), heterocyclic group (eg,
2-pyridyl group, 2-thiazolyl group, etc.) and the like. The substituted alkyl group preferably has 1 to 1 carbon atoms.
7, particularly preferably a sulfoalkyl group having 1 to 4 carbon atoms, and most preferably at least one of R ₄₁ and R ₄₂ is this sulfoalkyl group. Y represents an ion necessary for balancing the charge, n4 is 0 or 1, and 0 when forming an intramolecular salt.

Z₄₁And Z₄₂Are identical to each other
May also be different and may be fused with an aromatic ring
The group of non-metal atoms required to form the oxazole nucleus is shown.
You Z ₄₁And Z₄₂Oxazole nucleus formed by
The following may be mentioned as examples. Oxazole,
4-methyloxazole, 4-nitroxazole, 5
-Methyloxazole, 4-phenyloxazole,
4,5-diphenyloxazole, 4-ethyloxazo
Etc.), benzoxazole nucleus (benzoxazo)
5-chlorobenzoxazole, 5-methylbenzo
Oxazole, 5-bromobenzoxazole, 5-full
Orobenzoxazole, 5-phenylbenzoxazo
, 5-methoxybenzoxazole, 5-nitrobe
Nazoxazole, 5-trifluoromethylbenzox
Sazole, 5-hydroxybenzoxazole, 5-carb
Ruboxybenzoxazole, 6-methylbenzoxa
Zole, 6-chlorobenzoxazole, 6-nitrobe
Nzoxazole, 6-methoxybenzoxazole,
6-hydroxybenzoxazole, 5,6-dimethyl
Benzoxazole, 4,6-dimethylbenzoxazo
, 5-ethoxybenzoxazole), naphthooxy
Sazole nucleus (eg naphtho [2,1-d] oxazol
Naphtho [1,2-d] oxazole, naphtho [2,2
3-d] oxazole, 5-nitronaphtho [2,1-
d] oxazole), etc.
Or an unsubstituted benzoxazole nucleus,
Especially effective.

Q represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group,
Isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group, etc.). Q
The alkyl group represented by may be substituted, and examples of the substituted alkyl group include an aralkyl group (eg, benzyl group, 2-phenylethyl group), a hydroxyalkyl group (eg, 2-hydroxyethyl group, 3-hydroxy). Propyl group), carboxyalkyl group (for example, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group), alkoxyalkyl group (for example, 2-methoxyethyl group, 2- (2-
Methoxyethoxy) ethyl group), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3
-Sulfobutyl group, 4-sulfobutyl group, 2- [3-sulfopropoxy] ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group), sulfatoalkyl group (for example, 3-sulfato) Propyl group, 4-sulfatobutyl group), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group), 2-acetoxyethyl Group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group,
Allyl group) and the like. Q is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group), which has a large effect.

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

[0071]

[Chemical 8]

[0072]

[Chemical 9]

[0073]

[Chemical 10]

[0074]

[Chemical 11]

[0075]

[Chemical 12]

The compound of formula (IV) may be added at any time before the chemical sensitization step.
Specifically, a method of adding during the formation of silver halide grains,
A method of adding in the silver halide emulsion desalting step, a method of adding just before the silver halide emulsion chemical ripening (chemical sensitization) step,
There is a method of adding at the time of chemical ripening of silver halide emulsion, but preferably, the compound of the general formula (IV) is added before addition of the gold sensitizer or chalcogen sensitizer described above, that is, before chemical sensitization by these compounds. Is added. It is also possible to add the compound of the general formula (IV) at a temperature of 25 ° C. or higher and lower than 55 ° C., and then to raise the temperature above the addition temperature to carry out chemical ripening so that each halogenated grain can be uniformly attached.

The spectral sensitizing dyes represented by formula (IV) used in the present invention can be incorporated in the silver halide emulsion of the present invention by dispersing them directly in the emulsion or by adding water. , Methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
1-butanol, 1-methoxy-2-propanol,
It may be added to the emulsion by dissolving it in a solvent such as N, N-dimethylformamide alone or in a mixed solvent. Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, this solution is dispersed in water or a hydrophilic colloid, and this dispersion is dispersed in an emulsion. As described in JP-B-46-24185 and the like,
A method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to an emulsion.
-23389, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 5
As disclosed in US Pat. No. 7,220,91, a method in which a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is coexisted to form an aqueous solution and the solution is added to the emulsion, US Pat. , 822,135, U.S. Pat. No. 4,006,6
As described in Japanese Patent Application No. 025, etc., a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant into an emulsion is disclosed in JP-A-53-102733 and JP-A-58-105141. As described above, the dye is directly dispersed in the hydrophilic colloid, and the dispersion is added to the emulsion. As described in JP-A No. 51-74624, the dye is dissolved by using a compound for red-shifting. However, a method of adding this solution to the emulsion can also be used. Ultrasonic waves can also be used for dissolution.

[0078] In the present invention, the addition amount of the compound of general formula (IV) is a silver 1 0.2 × 10 ^-3 mol or more per mol 1.5 × 10 ^-3 mol, 0.2 × 10 ^{- It} is more preferably ³ mol or more and 1.2 × 10 ⁻³ mol or less. These dyes may be used alone or in combination of two or more.

In the silver halide photographic light-sensitive material of the present invention, in addition to the above-mentioned general formula (IV), a spectral sensitizing dye can be used in combination. The spectral sensitizing dyes that can be used in combination include, for example, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
Examples thereof include holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful spectral sensitizing dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
As the basic heterocyclic nucleus, any of the nuclei normally used for cyanine dyes can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus,
Selenazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, tellurazole nuclei; nuclei in which alicyclic hydrocarbon rings are condensed to these nuclei; and aromatics to these nuclei Nuclei in which a group hydrocarbon ring is condensed, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, benzothiazole nucleus, natophthiazole nucleus, benzoselenazole nucleus A nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzoterazole nucleus, etc. can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

For the merocyanine dye or the composite merocyanine dye, as the nucleus having a ketomethylene structure, any nucleus generally used for merocyanine dyes can be applied. Particularly useful nuclei include pyrazolin-5-one nuclei, thiohydantoin nuclei, and 2-thiooxazolidine-2,4-
Applying 5-membered and 6-membered heterocyclic nuclei such as dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus and 2-thioselenazolidine-2,4-dione nucleus You can

A combination of sensitizing dyes is often used especially for the purpose of supersensitization. A typical example is US Pat. No. 2,
688,545, 2,977,229, 3,3
97,060, 3,522,052, 3,52
No. 7,641, No. 3,617,293, No. 3,62
8,964, 3,666,480, 3,67
2,898, 3,679,428, 3,70
No. 3,377, No. 3,769,301, No. 3,61
4,609, 3,837,862, 4,02
6,707, British Patent Nos. 1,344,281 and 1,507,803, Japanese Patent Publication No. 43-493.
6, No. 53-12375, JP-A No. 52-11061.
No. 8 and No. 52-109925.

Furthermore, these sensitizing dyes are dyes that do not exhibit a spectral sensitizing effect by themselves, or substances that do not substantially absorb visible light and are combined with the sensitizing dyes to achieve remarkable spectral sensitization. It may be used in combination with any compound known to be called a so-called supersensitizer which exhibits an increase. Typical examples of the supersensitizer include bispyridinium salt compounds described in JP-A-59-142541, stilbene derivatives described in JP-B-59-18691, JP-B-49-46932 and the like. Water-soluble bromides such as potassium bromide, potassium iodide, etc., water-soluble iodides, US Pat. No. 3,743,51
Examples thereof include condensates of aromatic compounds and formaldehyde described in No. 0 specification, cadmium salts, azaindene compounds, and the like. The spectral sensitizing dye is added to the emulsion after chemical ripening or before chemical ripening. Most preferably, the spectral sensitizing dye is added to the silver halide grains of the present invention during or before chemical ripening (for example, during grain formation or physical ripening).

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) Tetraazaindene), many compounds known as antifoggants or stabilizers such as pentaazaindenes and the like can be added. For example, US Pat. Nos. 3,954,474 and 3,98
Nos. 2,947 and 52-28660 can be used. One of the preferred compounds is the compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers can be used in various forms before grain formation, during grain formation, after grain formation, in the desalting step, during dispersion after desalting, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose at the time.

In the present invention, it is also preferable to carry out chemical sensitization by coexisting a nucleic acid or a decomposition product thereof before the completion of chemical sensitization. Regarding nucleic acid or its degradation product, see Japanese Patent Laid-Open No.
The thing of 2-67541 can be used. The nucleic acid used in the present invention includes deoxyribonucleic acid (D
NA) and ribonucleic acid (RNA), and as nucleic acid degradation products, those in the middle of degradation, adenine, guanine,
Examples include simple substances such as uracil, cytosine and thymine. Adenine is mentioned as a particularly preferable nucleic acid decomposition product. These can be used alone or in combination. In this case, it goes without saying that the nucleic acid and the nucleic acid decomposition product may be used in combination. The amount of the nucleic acid or its decomposition product added varies depending on the kind of the nucleic acid decomposition product, but is in the range of 20 mg or more, preferably 100 mg to 1 g, per mol of silver halide. When these nucleic acids or nucleic acid decomposition products are used alone or in combination of two or more as described above, the total amount added is sufficient.

In the light-sensitive material of the present invention, a crossover light-cutting layer may be provided between the light-sensitive emulsion layer and the support, if desired, for the purpose of making an image clear. A dye corresponding to the photosensitive wavelength range is added to the crossover light cut layer. Any dye can be used as long as it does not leave harmful absorption after development processing. A method for adding a dye in a solid fine particle dispersion state is described in JP-A-2-26493.
6, JP-A-3-210553, JP-A-3-2105
54, JP-A-3-238447, and JP-A-4-140.
38, JP-A-4-14039, and JP-A-4-1256.
35, JP-A-4-338747, JP-A-6-275.
89, etc. The dyes that can be used include, for example, the compounds of the general formula (I) described in JP-A-4-211542.
(VII) Dye, Compound Examples I-1 to I-37, II-
1-II-6, III-1 to III-36, IV-1 to
IV-16, V-1 to V-6, VI-1 to VI-13,
VII-1 to VII-5. Dyes of general formula (1) described in JP-A-8-73767, compound examples 1 to 6. JP-A-8-8
No. 7091 of the general formulas (VIII) to (XII), compound examples VIII-1 to VIII-5, IX-1 to
IX-10, X-1 to X-21, XI-1 to XI-6,
XII-1 to XII-7.

In addition to these, a known dye is adsorbed on a mordant, a known dye is dissolved in oil and emulsified and dispersed in the form of oil droplets, and a dye described in JP-A-3-5748 is adsorbed on the surface of an inorganic substance. The method, the method of adsorbing the dye described in JP-A-2-298939 to the polymer, and the like can also be used. As a method of adding the crossover light cut layer to the light-sensitive material, those described in each specification can be used.

A dye may be added to the light-sensitive material of the present invention for the purpose of detecting the position of the light-sensitive material. The dye preferably has an absorption spectrum according to the maximum sensitivity wavelength of the detection sensor, and any dye may be used as long as it does not leave harmful absorption after the development processing. Preferably, a dye having an absorption maximum at 700 nm to 1400 nm or a fine particle dispersion thereof is used. For example, (1) water-soluble dyes that are decolorized during treatment include cyanine dyes, pyrylium dyes and aminium dyes of general formulas (I) to (IV) described in JP-A-3-211542, compound examples I-1 to I- 6, II-1 to II-4, III-
1 to III-4, IV-1 to IV-5.

(2) Solid fine particle disperse dyes that are decolorized during treatment include cyanine dyes of formulas (I) to (IV), pyrylium dyes and aminium dyes described in JP-A-3-138640, Compound Example I-1. ~ I ~ 28, II
-1 to II-10, III-1 to III-6, IV-1
~ IV-7.

(3) As the dye that is not decolorized during the treatment, tricarbocyanine dyes having a carboxyl group of the general formula (I) to the general formula (II) described in Japanese Patent Application No. 6-227983, Compound Examples 1 to 33. Japanese Patent Application No. 6-2792
Tetracarbocyan dyes having a carboxyl group of the general formula (I) to the general formula (II) described in No. 97, compound examples 1 to 19. A cyanine dye having no acid group of the general formula (1) to the general formula (3) described in Japanese Patent Application No. 7-208569.
Compound Examples 1-63. General [1] lake type cyanine dyes described in JP-A-8-333519, Compound Example No. 1 to
No. 37.

In addition to these, JP-A-62-299959
Pyrylium dye, light-scattering particles described in JP-A-63-131135, cyanine dye described in JP-A-1-266536, solid fine particle dispersion of oxonol dye described in JP-A-2-282244, JP-A-3- 136038
Holopolar type cyanine dye described in JP-A-7-253
No. 639, polymer type cyanine dyes, JP-A-7-1
13072, tin-doped indium oxide (IT
O) powder and the Yb ³⁺ compound described in JP-A-9-5913 can also be used.

A dye for the purpose of detecting the position of the light-sensitive material,
As the method of adding to the light-sensitive material, those described in each specification can be used.

A dye may be added to the light-sensitive material of the present invention for the purpose of improving the color tone of a silver image. The dyes are pyrazoloazole dyes, anthraquinone dyes, azo dyes, azomethine dyes, oxonol dyes, carbocyanine dyes,
Among the styryl dyes, triphenylmethane dyes, indoaniline dyes and indophenol dyes, those having a predetermined absorption maximum wavelength are selected. Among them, anthraquinone dyes of general formula (I) described in JP-A-5-34858 and general formula (I) described in JP-A-4-247449.
And the azomethine dyes of the general formula (I) described in JP-A-4-296845, the indoaniline dyes contained in the general formula (I) described in JP-A-5-43809, and the JP-A-5-43809.
The azo dyes described in No. 341441 are useful.

Specific examples of anthraquinone dyes include compounds 1 to 9 described in JP-A-5-341441 and JP-A-5-
Compounds 3-6 to 3-18 and 3 described in 165147
-23 to 3-38 can be used. As the azomethine dye, specifically, compounds 17 to 46 described in JP-A-5-341441 can be used. As the indoaniline dye, specifically, compounds 11 to 19 described in JP-A-5-289227, compound 47 described in JP-A-5-341441 and compounds 2-10 to 2-11 described in JP-A-5-165147 are used. can do. As the azo dye, specifically, compounds 10 to 16 described in JP-A-5-341441 can be used.

A dye for the purpose of improving the color tone of a silver image,
As the method of adding to the light-sensitive material, those described in each specification can be used.

The light-sensitive material of the present invention may contain colloidal silica. Colloidal silica has an average particle size of 1 to 1000 nm, preferably 5 to 500 n.
m, more preferably 5 to 100 nm, the main component of which is silicon dioxide, and may contain alumina, sodium alginate, or the like as a minor component.

A specific example of the colloidal silica is Snowtex 2 under the trade name of Nissan Chemical Co., Ltd. (Tokyo, Japan).
0, Snowtex 30, Snowtex C, Snowtex O and the like.

The layer containing colloidal silica in the light-sensitive material of the present invention includes a surface protective layer, an intermediate layer, a silver halide emulsion layer, an antihalation layer, an undercoat layer, a filter layer,
Although it may be any hydrophilic colloid layer such as a backing layer,
Especially for the purpose of pressure resistance, it is preferably contained in the surface protective layer or the silver halide emulsion layer.

The content of colloidal silica is preferably 1 to 200% by mass, and more preferably 10 to 100% by mass based on the mass of the hydrophilic colloid in the contained hydrophilic colloid layer.
Is most preferred.

In the layer containing colloidal silica, it is preferable to contain a plastic polymer latex in combination, if necessary.

Any layer of the photographic light-sensitive material of the present invention may contain a polymer latex obtained by polymerizing a hardly water-soluble monomer.

As such a monomer, for example, acrylic acid esters, methacrylic acid esters, divinylbenzene and the like described in JP-A No. 7-230135, page 2, line 2, line 5 to line 17 can be used.

In such a polymer latex, the above-mentioned monomer may be copolymerized with another monomer, and the monomer at this time is, for example, 2 of JP-A-7-230135.
The monomers described on page 2, 2nd line, line 32 to page 1, 1st line, 35th line can be used, and among them, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes, and olefins are preferable. Used.

Examples of the polymer latex include, for example, Lx-1 to Lx-21 of JP-A-7-230135.
Is mentioned.

In the present invention, No. 1 described in Example 1 of JP-A-6-194779 is used. 1-No. The matting agent of 8 can be preferably used. In addition, JP-A-6-13857
Preferred compound examples 1 to 9 described in paragraph 0023 of No. 2 can be preferably used.

With respect to the size and the like of these matting agents, the sizes and amounts used described in paragraph 0049 of JP-A-6-194779 can be preferably used. Again 2
It is possible to mix and use matting agents having different particle sizes. Regarding the particle size distribution of the matting agent, monodisperse particles having a coefficient of variation of 3 to 30% can be used or polydisperse particles having a coefficient of variation of 30% or more can be used depending on the purpose.

The preferable coating amount of the emulsion of the silver halide photographic light-sensitive material of the present invention is, in terms of silver, per 1 m ^{2 on} one side,
It is 2.0 g or less. Preferably 0.5 g or more 1.7
g or less. More preferably 0.8 g or more and 1.5 g
It is the following.

The coating amount of total gelatin in the hydrophilic colloid layer of the light-sensitive material of the present invention is 2.5 g or less (total coating amount per one side), 0.5 g / m ² or less and 2.5 g / m ² or less. Is preferable, and particularly preferably 1.0 g / m ² or more and 2.1.
g / m ² or less. In this case, the gelatin coating amount of the protective layer is preferably 0.2 g / m ² or more and 1.0 g / m ² or less.

In the present invention, the swelling ratio of the light-sensitive material is defined as a value obtained by subtracting the film thickness value in the dry state from the film thickness value after the light-sensitive material is immersed in distilled water at 21 ° C. for 3 minutes. A value obtained by dividing the value by the film thickness value in the dry state is multiplied by 100, and is defined as (%) and can be obtained. The range of the swelling ratio is preferably 20% to 220%, more preferably 4
It is 0% or more and 150% or less.

Generally, a silver halide photographic light-sensitive material is prepared by coating a water-soluble coating solution containing a hydrophilic colloid such as gelatin as a binder on a support and then in a low-temperature air having a dry-bulb temperature of -10 ° C to 20 ° C. It is cooled and solidified in the following, and then it is dried by raising the temperature. The weight ratio of gelatin to water immediately after coating is usually around 3000%.

The coating solution usually contains various additives such as hydrophilic colloid binder, silver halide particles, surfactant, plasticizer such as polymer latex, gelatin hardening agent, dye, sensitizing dye, matting agent and the like. include.

In the present invention, when the hydrophilic colloid layer coating solution is applied and then dried, the water content becomes 100% or less based on the dry weight of the binder of all the coating layers having the silver halide emulsion layer. It is preferable to dry at a wet bulb temperature of 20 ° C. or lower, preferably 19 ° C. to 10 ° C.

When two or more hydrophilic colloid layers are simultaneously coated and dried (that is, when the coating layers to be dried are two or more layers), the water content is the sum of the water content of all layers. The binder dry weight represents the sum of the binder dry weight (dry weight) of all layers.

The wet-bulb temperature is the temperature of water droplets in the equilibrium state of moist air, and the lower the humidity of air, the lower the temperature. During the constant rate drying period of the drying step, the wet-bulb temperature of the drying air is almost equal to the surface temperature of the coated sample.

The environmental conditions at the time of winding into a roll after coating and drying are such that the absolute humidity is 1.4% by mass or less, preferably 1.3 to 0.6% by mass. In the present invention, the product processing of the silver halide photographic light-sensitive material wound up in a roll after coating and drying is performed under an environment where the absolute humidity is 1.4% by mass or less, preferably 1.3 to 0.6% by mass. It is preferably processed.

The absolute humidity (wt%) represents the condition of moist air, and is a ratio of the amount of water vapor (kg) in the moist air to the mass (kg) of dry air in the moist air expressed as a percentage. .

The silver halide photographic light-sensitive material is put in a moistureproof package, and its mouth is heated so that the absolute humidity in the package is 1.4% by mass or less, preferably 1.1 to 0.6. It means that the light-sensitive material is in equilibrium at the above absolute humidity after being sealed by a method such as a seal.

Further, after processing, the absolute humidity is 1.4% by mass.
It is particularly preferable to perform the seasoning in the following environment and then heat-seal-seal the package in the same environment.

There are no particular restrictions on the various additives used in the silver halide photographic emulsion and the silver halide photographic light-sensitive material of the present invention. For example, those described in the following relevant parts of JP-A-2-68539 are used. be able to.

Item Applicable place 1. Silver halide emulsion and its manufacturing method JP-A-2-68539, page 8, lower right column, line 6 from the bottom to page 10, upper right column, line 12 2. Chemical sensitization method, page 10, upper right column, item 13 to lower left column, line 16 3. Antifoggants / stabilizers, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column, 4. Spectral sensitizing dye, page 4, lower right column, line 4 to page 8, lower right column. 5. Surfactants / antistatic agents, page 11, upper left column, line 14 to page 12, upper left column, line 9 6. Matting agent / slip agent Page 12, upper left column, line 10 to upper right column, line 10 Plasticizer, page 14, lower left column, line 10 to lower right column, line 1 7. Hydrophilic Colloid, page 12, upper right column, line 11 to lower left column, line 16 8. Hardener, page 12, lower left column, line 17 to page 13, upper right column, line 6 9. Support, page 13, upper right column, lines 7 to 20. 10. Dyes and mordants, page 13, lower right column, line 1 to page 14, lower left column, line 9

The silver halide emulsion of the present invention can be used in all conventionally known photographic light-sensitive materials. Examples of such a silver halide photographic light-sensitive material, including the silver halide photographic light-sensitive material of the present invention, include black and white silver halide photographic light-sensitive materials (for example, X-ray sensitive materials, printing sensitive materials, photographic papers, negatives). Film, micro film, direct positive sensitive material,
Ultrafine particle dry plate sensitive material (for LSI photomask, shadow mask, liquid crystal mask)], color photographic light-sensitive material (eg negative film, photographic paper, reversal film, direct positive color light-sensitive material, silver dye bleaching method photo) be able to. Further, a diffusion transfer type photosensitive material (for example, a color diffusion transfer element, a silver salt diffusion transfer element), a photothermographic material (black and white, color), a high density digital recording light sensitive material, a holographic light sensitive material and the like can be mentioned.

In the photographic light-sensitive material of the present invention, the following phosphors are used as a fluorescent intensifying screen, and X-ray photography can be preferably carried out.

Blue emitting phosphor Y ₂ O ₂ S: Tb, LaOBr: Tb, BaFCl: Eu Green emitting phosphor Gd ₂ O ₂ S: Tb, LaO ₂ S: Tb

As the UV-emitting phosphor, M'phase YTaO is used.
₄ alone or Gd, Bi, Pb, Ce, Se, Al,
Compounds containing Rb, Ca, Cr, Cd, Nb, etc.,
A compound obtained by adding Gd, Tm, Gd and Tm, Gd and Ce, Tb to LaOBr, a compound obtained by adding HfZr oxide alone or Ge, Ti alkali metal, etc.,
Y ₂ O ₃ alone or a compound to which Gd or Eu is added, Y ₂
Compounds of Gd added to O ₂ S, G as the base material of various phosphors
Examples include compounds using d, Tl, and Ce as activators. Particularly preferred compounds include M'phase YTaO ₄ alone or a compound containing Gd and Sr, a compound containing Gd, Tm, Gd and Tm added to LaOBr, and HfZ.
It is an oxide of r or a compound to which Ge, Ti alkali metal or the like is added.

The particle size of the phosphor is preferably 1 μm or more and 20 μm or less, but can be changed depending on the required sensitivity and manufacturing problems. The coating amount is 400 g / mm ² or more and 2000 g / mm ²
The following is preferable, but it cannot be said unconditionally depending on the required sensitivity and image quality. A single intensifying screen may be used to provide a particle size distribution from the vicinity of the support to the surface. In this case, it is generally known to increase the size of particles on the surface. The space filling rate of the phosphor is 40% or more, preferably 60% or more.

When the phosphor layers are provided on both sides of the photosensitive material for photographing, the phosphor coating amount on the X-ray incident side and the opposite side can be changed. It is generally known to reduce the coating amount of the intensifying screen on the X-ray incident side, especially when a high-sensitivity system is required because of shielding by the intensifying screen on the X-ray incident side.

The support used in the screen used in the present invention may be paper, metal plate, polymer sheet or the like, but a flexible sheet such as polyethylene terephthalate is generally used. The support may be added with a reflecting agent or a light absorbing agent, or may be provided as a separate layer on the surface, if necessary.

If necessary, the surface of the support may be slightly uneven, or an adhesive layer for increasing the adhesion to the phosphor layer or a conductive layer may be provided as an undercoat. Examples of the reflecting agent include zinc oxide, titanium oxide, and barium sulfate. Titanium oxide and barium sulfate are preferable because the phosphor has a short emission wavelength. The reflecting agent may be present not only in the support or between the support and the phosphor layer, but also in the phosphor layer. When it is present in the phosphor layer, it is preferably localized near the support.

As the binder used in the screen of the present invention, proteins such as gelatin, polysaccharides such as dextran and corn starch, natural polymer substances such as gum arabic; polyvinyl butyral, polyvinyl acetate, polyurethane, polyalkyl acrylate, chloride Examples include synthetic polymer substances such as vinylidene, nitrocellulose, fluorine-containing polymers, polyesters, and mixtures and copolymers thereof. As a preferable binder,
The basic performance is high transmittance for light emitted from the phosphor. In this respect, gelatin, corn starch, an acrylic polymer, a fluorine-containing olefin polymer, a polymer containing a fluorine-containing olefin as a copolymer component, a styrene / acrylonitrile copolymer and the like can be mentioned. These binders may have functional groups that are crosslinked by the crosslinking agent. Further, depending on the required image quality performance, an absorber for the light emitted from the phosphor may be added to the binder, or a binder having a low transmittance may be used. Examples of the absorber include pigments, dyes, and ultraviolet absorbing compounds. The ratio of phosphor to binder is generally 1: 5 to 50: 1 by volume, preferably 1: 1 to 1: 5: 1. The ratio of the phosphor to the binder may be uniform or non-uniform in the thickness direction.

The phosphor layer is usually formed by a coating method using a coating liquid in which the phosphor is dispersed in a binder solution.
Examples of the solvent for the coating liquid include water, alcohols, chlorine-containing hydrocarbons, organic solvents such as ketones, esters and ether aromatic compounds, and mixtures thereof.

In the coating liquid, dispersion stabilizers such as phthalic acid, stearic acid, caproic acid, and surfactants for phosphor particles, and plasticizers such as phosphoric acid ester, phthalic acid ester, glycolic acid ester, polyester, and polyethylene glycol are used. Agents may be added.

In the screen used in the present invention, a protective layer can be provided on the phosphor layer. As the protective layer, a method of coating on the phosphor layer, or a method of separately preparing and laminating a protective layer film is generally used. In the coating method, the phosphor layer may be coated at the same time, or the phosphor layer may be coated and dried before coating. The protective layer may be the same substance as the binder of the phosphor layer, or may be a different substance. Examples of the substance used for the protective layer include substances listed as the binder for the phosphor layer, as well as cellulose derivatives, polyvinyl chloride, melamine, phenol resins, and epoxy resins.
Preferred materials include gelatin, corn starch, acrylic polymers, olefin polymers containing fluorine, polymers containing olefins containing fluorine as a copolymer component, styrene / acrylonitrile copolymers, and the like. The thickness of the protective layer is generally 1 μm or more 2
It is preferably 0 μm or less and 2 μm or more and 10 μm or less, and 2
More preferably, it is not less than μm and not more than 6 μm. It is preferable to emboss the surface of the protective layer of the present invention. In addition, a matting agent may be present in the protective layer, or a substance having a light-scattering property for light emission depending on the image to be obtained, such as titanium oxide, may be present.

A surface slipperiness may be imparted to the protective layer of the screen used in the present invention. Examples of preferable slip agents include polysiloxane skeleton-containing oligomers and perfluoroalkyl group-containing oligomers.

Electrical conductivity may be imparted to the protective layer of the present invention. Examples of the conductivity imparting agent include white and transparent inorganic conductive substances and organic antistatic agents. Preferred inorganic conductive materials include ZnO powder, whiskers, and Sn.
Examples include O ₂ and ITO.

The development processing method of the present invention is described in US Pat. No. 5,498,511, JP-A-7-16832, JP-A-8-54712, JP-A-9-329875, and JP-A-10-26815. Can be used as a reference.

The developer for processing the light-sensitive material of the present invention contains
It is preferable to use hydroquinone, ascorbic acid or erythorbic acid (diastereomeric ascorbic acid) and / or their derivatives.

Ascorbic acid and / or derivatives thereof used in the present invention include US Pat. No. 2,688,549.
Japanese Patent Publication No. 36-17599, JP-A-3-24975.
No. 6, JP-A-4-270343 and the like.

Specifically, compounds described in US Pat. No. 2,688,549, page 1, column 1, line 22 to page 1, column 2, line 33, JP-B-36-17.
No. 599, page 1, left column, lines 21 to 26, compounds I-1 to I-8 and II-1 to II described on page 4, JP-A-3-249756.
-4, the compounds described in JP-A-4-270343, page 4, column 5, lines 40 to 50 can be used.

Of these, ascorbic acid or erythrubic acid (diastereomers of ascorbic acid) and their alkali metal salts such as lithium salt, sodium salt and potassium salt are preferable.

The developing agent is usually 0.01 mol / liter or more.
It is preferably used in an amount of 0.8 mol / l,
It is particularly preferable to use it in an amount of 0.1 mol / liter to 0.4 mol / liter.

In the present invention, it is desirable to use together with a developing agent as an auxiliary developing agent exhibiting superadditivity.

The auxiliary developing agent exhibiting superadditivity is 1-
There are phenyl-3-pyrazolidones auxiliary developing agents.

1-Phenyl-3-pyrazolidones as auxiliary developing agents 1-phenyl-3-pyrazolidone, 1-
Phenyl-3-pyrazolidone, 1-phenyl-4,4-
Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-P-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and so on. Of these, 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone is preferred.

In the present invention, when a 1-phenyl-3-pyrazolidone type auxiliary developing agent is used in combination with the developing agent, 0.001 mol / liter to 0.1 is used.
It is preferably used in an amount of mol / l, particularly preferably the latter in an amount of 0.005 mol / l to 0.05 mol / l.

As an auxiliary developing agent exhibiting superadditivity, there is a p-aminophenol type auxiliary developing agent.

P-Aminophenols As auxiliary developing agents, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-
Hydroxyphenyl) -glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like are available, but N-methyl-p-aminophenol is preferred.

In the present invention, when a p-aminophenol type auxiliary developing agent is used in combination with the developing agent, it is preferably used in an amount of 0.001 mol / liter to 0.1 mol / liter, particularly the latter. To 0.0
It is preferably used in an amount of 05 mol / liter to 0.05 mol / liter.

As the antifoggant added to the developing solution,
Azole compounds (for example, benzothiazolium, benzimidazolium, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.),
Mercapto compounds (for example, mercaptothiazoles, mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc.) .

Particularly, benzotriazoles include 5-
Examples include methylbenzotriazole, 5-bromobenzotriazole, 5-chlorobenzotriazole, 5-butylbenzotriazole, benzotriazole and the like. As nitroindazoles, 5-nitroindazole, 6
-Nitroindazole, 4-nitroindazole, 7-
Nitroindazole, 3-cyano-5-nitroindazole or the like can be used.

In the present invention, as a silver stain preventing agent in a developing solution, JP-B-56-46585 and JP-B-62-4702 are used.
No. 4, Japanese Patent Publication No. 62703/1987, and US Pat. No. 4,225,221.
5, U.S. Pat. No. 3,318,701, JP-A-58-20.
3439, JP-A-62-56959, JP-A-62-
No. 178247, JP-A 1-200249, JP-A-5
The compounds described in JP-A-503179 and JP-A-5-53257 can be used.

As a fixing accelerator, Japanese Examined Patent Publication (Kokoku) No. 45-357.
54, JP-A-58-122535 and JP-A-58-122.
536, thiourea derivatives, alcohols having a triple bond in the molecule, thioethers described in US Pat. No. 4,126,459, or anion-free cyclodextran ethers, crown ethers, diazacycloundecene and di ( Hydroxyethyl) butamine and the like. JP-A-7-5654 and 6-273898.
Can include the mesoionic compound described in No.

As a mildew-proofing means, JP-A-60-2639 is used.
Ultraviolet irradiation method described in No. 39, 60-263940
Using the magnetic field described in No. 61-131632
Method using the ion exchange resin described in No.
The methods using the antibacterial agents described in JP-A-61-115154, JP-A-62-153952 and JP-A-62-120951 and JP-A-62-1209532 can be used in combination.

Furthermore, L. F. West, “Water
Quality Criteria ", Photo.
Sci. & Eng. , Vol. 9 (1965), M.A.
W. Each, "Microbiological
Growth in Motion-picture
Processing ”, SMTPE Journal
Vol. 85 (1976), R.I. D. Deega
n, "Photo Processing Wash
Water Biocides ”, J. Imaging
Tech. , Vol. 10, No. 6 (1984) and JP-A-57-8542, 57-58143,
58-105145, 57-132146, 58-18631, 57-97530, 57-.
157244, JP-A-6-118583, and 8-2.
Antibacterial agents, antifungal agents, surfactants and the like described in No. 48589 can be used in combination.

Further, in the washing bath or stabilizing bath, R.
T. Kreinman, J. Am. Image. Tec
h. , 10 (6), p. 242 (1984), isothiazoline compounds, Research Disc.
Loss, Volume 205, No. 20526 (198
(Issue May, 1), isothiazoline compounds, vol. 228, no. 22845 (April 1983), isothiazoline compounds, JP-A-62-20
The compounds described in No. 9532 are used as antibacterial agents (Micro
It can also be used together as a biocide).

Others, "Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Mitsui Publishing (Showa 57), "Handbook of Antibacterial and Antifungal Technology"
Compounds such as those described in the present Society for Antibacterial and Antifungal, Hakuhodo (Showa 61) may be included.

Further, a part or all of the overflow from the washing or stabilizing bath caused by replenishing the washing or stabilizing bath with antifungal water according to the treatment is described in JP-A-60-235133. As described, it can also be used for the pretreatment step of diluting the processing solution having fixing ability.

In the processing system of the present invention, the carry-out amount of the liquid carried out by the photosensitive material from the developing tank to the fixing tank and from the fixing tank to the water washing tank is 0.01 ml per 4 sheets.
2ml or less is preferable, 0.1ml or more and 1.2ml
The following is preferable, and 0.1 ml or more and 0.1 is more preferable.
It is preferably 8 ml or less.

When the washing tank is multi-tiered, the carry-out amount from the washing tank to the washing tank is 0.1 m per 4 pieces.
1 to 2 ml is preferable, 0.1 to 1.2 m
It is more preferably 1 or less. More preferably, 0.1 ml or more and 0.8 ml or less is preferable.

The carry-out amount of the wash water when entering the drying zone from the wash tank is preferably 0.1 ml or more and 2 ml or less, more preferably 1 ml or less, and further preferably 0.5 ml per 4 sheets of sensitive material. It is the following.

The light-sensitive material of the present invention is suitable for rapid processing, and the total processing time (Dry to Dry) from the time when it is carried into the developing tank to the end of the drying step is 90 seconds or less, further 5 to 60 seconds. Preferably there is.

The development in this case is 5 to 30 at 25 to 40 ° C.
Sec., Fixing at 25-40 ° C. for 5-40 seconds, washing with water 0-40
It is preferable to perform the drying at 40 ° C. for 5 to 30 seconds and the drying at 40 to 120 ° C. for 1 to 30 seconds. The replenishing amount is 30 to 650 ml of developer and 30 to 650 m of fixer per 1 m ² of the light-sensitive material.
It is preferable that the volume of the washing water is 30 to 50,000 ml.

For details of such processing, reference can be made to the description in the above-mentioned Japanese Patent Laid-Open No. 9-329875.

[0162]

EXAMPLES The present invention will be described below with reference to examples. Example 1 (Preparation of comparative silver halide emulsion-1) KBr 0.8 g,
1178 mL of an aqueous solution containing 3.2 g of gelatin having an average molecular weight of 20,000 was kept at 35 ° C. and stirred. AgNO
₃ (1.6 g) aqueous solution, KBr (1.16 g) aqueous solution, and gelatin (1.1 g) aqueous solution having an average molecular weight of 20,000 were added by the triple jet method over 45 seconds. AgN
The concentration of the O ₃ solution was 0.3 mol / liter. Then, the temperature was raised to 75 ° C over 20 minutes, and the average molecular weight was 1
26 g of 00000 gelatin was added. AgNO
₃ (209 g) aqueous solution and KBr aqueous solution were added over 75 minutes while the flow rate was accelerated by the control double jet method while maintaining pAg at 8.0. Average molecular weight 1000
After gelatin of 00 was added, it was desalted in a conventional manner. Then, gelatin having an average molecular weight of 100,000 was added and dispersed, and the pH was adjusted to 5.8 and pAg 8.0 at 40 ° C. to prepare an emulsion. This emulsion contains 1 mol of Ag and 60 g of gelatin per kg of emulsion, and the silver halide emulsion grains have an average equivalent circle diameter of 1.1 μm, a variation coefficient of equivalent circle diameter of 20%, an average thickness of 0.16 μm, and an average aspect ratio. Ratio 6.
It was 9 tabular grains. The particle shape was measured by observing a transmission electron micrograph image of a replica of the particles.

(Preparation of silver halide emulsion A-1) KBr
1178 mL of an aqueous solution containing 0.8 g and 3.2 g of gelatin having an average molecular weight of 20,000 was kept at 35 ° C. and stirred. Ag
A NO ₃ (1.6 g) aqueous solution, a KBr (1.16 g) aqueous solution, and a gelatin (1.1 g) aqueous solution having an average molecular weight of 20,000 were added over 45 seconds by the triple jet method. A
The concentration of the gNO ₃ solution was 0.3 mol / liter. Thereafter, the temperature was raised to 75 ° C. over 20 minutes, and 26 g of gelatin having an average molecular weight of 100,000 was added. AgNO
₃ (209 g) aqueous solution and KBr aqueous solution were added over 75 minutes while maintaining the pAg at 8.5 while accelerating the flow rate by the control double jet method. Average molecular weight 1000
After gelatin of 00 was added, it was desalted in a conventional manner. Then, gelatin having an average molecular weight of 100,000 was added and dispersed, and the pH was adjusted to 5.8 and pAg 8.0 at 40 ° C. to prepare an emulsion. This emulsion contains 1 mol of Ag and 60 g of gelatin per kg of emulsion. The silver halide emulsion grains have an average equivalent circle diameter of 1.2 μm, a variation coefficient of equivalent circle diameter of 21%, an average thickness of 0.12 μm, and an average aspect ratio. Ratio 10
It was a tabular grain of

(Preparation of silver halide emulsion B-1) KBr
1178 mL of an aqueous solution containing 0.8 g and 3.2 g of an oxidation-treated gelatin having an average molecular weight of 20,000 was kept at 35 ° C. and stirred. AgNO ₃ (1.6 g) aqueous solution and KBr (1.1
6 g) aqueous solution and an oxidation-treated gelatin (1.1 g) aqueous solution having an average molecular weight of 20,000 were added by the triple jet method over 45 seconds. AgNO ₃ solution has a concentration of 0.3 mol
/ Liter of solution was used. 75 ℃ over 20 minutes
The temperature was raised to, and 26 g of gelatin having an average molecular weight of 100,000 was added. An AgNO ₃ (209 g) aqueous solution and a KBr aqueous solution were added over 75 minutes while the flow rate was accelerated by the control double jet method while maintaining the pAg at 8.5.
After adding gelatin having an average molecular weight of 100,000, it was desalted in a conventional manner. Then, gelatin with an average molecular weight of 100,000 was added and dispersed, and the pH was 5.8 at 40 ° C. and pAg.
The emulsion was adjusted to 8.0. This emulsion is emulsion 1k
A silver halide emulsion grain containing 1 mol of Ag and 60 g of gelatin per g, and having a mean equivalent circle diameter of 1.5 μm, a variation coefficient of the equivalent circle diameter of 22%, an average thickness of 0.10 μm and an average aspect ratio of 15 It was a particle.

(Preparation of silver halide emulsion C-1) KBr
1178 mL of an aqueous solution containing 0.8 g and 3.2 g of an oxidation-treated gelatin having an average molecular weight of 20,000 was kept at 35 ° C. and stirred. AgNO ₃ (1.6 g) aqueous solution and KBr (1.1
6 g) aqueous solution and an oxidation-treated gelatin (1.1 g) aqueous solution having an average molecular weight of 20,000 were added by the triple jet method over 45 seconds. AgNO ₃ solution has a concentration of 0.3 mol
/ Liter of solution was used. 75 ℃ over 20 minutes
Gelatinized with an average molecular weight of 100,000
6 g was added. AgNO ₃ (209g) aqueous solution and KB
The r aqueous solution was added over 75 minutes while accelerating the flow rate by the control double jet method while maintaining the pAg at 8.5. After adding gelatin with an average molecular weight of 100,000,
It was desalted in a conventional manner. Then, the average molecular weight is 10,000
0 gelatin was added and dispersed, and the pH was 5.8 at 40 ° C, p
The emulsion was adjusted by adjusting to Ag 8.0. This emulsion contains 1 mol of Ag and 60 g of gelatin per kg of emulsion, and the silver halide emulsion grains have an average equivalent circle diameter of 1.8 μm.
m, variation coefficient of circle equivalent diameter 22%, average thickness 0.08μ
It was a tabular grain having m and an average aspect ratio of 23.

(Chemical sensitization) Each emulsion prepared as described above was chemically sensitized while being kept at 56 ° C. with stirring. First, the following thiosulfonic acid compound-I was added in an amount of 10 ⁻⁴ mol per mol of silver halide, and then AgI fine particles having a diameter of 0.03 μm were added in an amount of 0.15 with respect to the total silver amount.
Mol% was added. After 3 minutes, add 1 × 10 ^-6 thiourea dioxide.
Mol / mol Ag was added, and the mixture was held for 22 minutes to carry out reduction sensitization. Then 4-hydroxy-6-methyl-1,
3,3a, 7-Tetraazaindene was added in an amount of 3 × 10 ^-4 mol per mol of silver halide to prepare a sensitizing dye IV-
The dispersion of No. 1 was used as the amount of the sensitizing dye IV-1 and was equivalent to 1 × 10 ⁻³ mol per mol of silver halide.
1.0 and 1 per mol of silver halide
0 ⁻⁴ mol, 3.0 × 10 ⁻⁵ mol equivalent, and calcium chloride were further added.

Subsequently, sodium thiosulfate was added in an amount of 6 × 10 ^-6 mol per mol of silver halide and selenium compound-1.
^Was added in an amount of 4 × 10 ^-6 mol per mol of silver halide, and then chloroauric acid was equivalent to 1 × 10 ^-5 mol per mol of silver halide and potassium thiocyanate was 2 × 10 ⁻ per mol of silver halide. ³ mol equivalent was added. Further, nucleic acid (manufactured by Sanyo Kokusaku Pulp Co., Ltd .: trade name RNA-F) was added in an amount of 67 mg per mol of silver halide. After 40 minutes, 1 × water-soluble mercapto compound-1 was added per mol of silver halide.
10 ^-4 mol equivalent was added and the mixture was cooled to 35 ° C. Thus, the chemical sensitization of the emulsion was completed.

[0168]

[Chemical 13]

The emulsions shown in Table 1 below were prepared using the compounds of the present invention (compounds represented by the general formulas (I), (II) and (III)). Was prepared in the same manner as Comparative Emulsion-1 and Emulsions A-1 to C-1 except that the addition time and amount shown in Table 1 were added.

[0170]

[Table 1]

(Preparation of Dye Layer Coating Solution) Each component of the dye layer (crossover cut layer) coated as an emulsion lower layer is
The coating liquid was prepared so that the coating amount was as follows.

(Preparation Method of Dye for Crossover Cut) 150 m of methanol to Dye A (solid 10 g)
while controlling the temperature at 70 ° C. in a mixed solvent of 1 and 50 ml of water, 2
The mixture was stirred for a time to prepare a wet cake dye of water. As a result, 1 mol of methanol and 2 mol of water were contained in 1 mol of the dye in the dye crystals. As a method for confirming the crystal solvent, the wet cake was dried at room temperature for measurement, and ¹ H
-The presence of methanol in the crystals could be confirmed by NMR. The presence of water of crystallization could be confirmed by Karl Fischer titration. It was also confirmed that when this crystal was heated at 150 ° C., methanol and water of crystallization in the crystal were released. From this, the solid concentration of dye in the wet cake was 50% by mass.

(Preparation Method of Aqueous Crystalline Dispersion of Crossover Cut Dye) The above wet cake dye was treated as a wet cake without being dried, and 3.0 g of the dye solid was weighed. Water for dispersion and 1.2 g of a 25% by mass solution of DEMOL SNB (manufactured by Kao Corporation) as a dispersant were mixed in advance, and the above dye was added to the mixture so that the total amount became 30 g. After adjustment, they were mixed well to form a slurry. Prepare 120 g of zirconia beads, put them in a vessel together with the slurry, and make a 1/16 gallon sand grinder mill (made by AIMEX Co., Ltd.).
At 1500 rpm, the vessel was water-cooled and dispersed. The average particle size of zirconia beads is 1 mm
The dispersion time was 8 hours. After the dispersion was completed, water was added so that the solid content concentration of the dye was 5% by mass, and the dispersion was taken out. This dye dispersion was designated as DP1.

(Method for Preparing Crossover Cut Layer Coating Liquid) Each compound was added to the water mother liquor so that the coating amount was as follows. The coating amount of the material per 1 m ^{2 on} one side was described in the order of addition of each compound. -Gelatin 0.47g-DP1 (dispersion liquid of dye for crossover cut) 8.4mg as dye solid content-Sodium polystyrene sulfonate (average molecular weight 600,000) 10mg-A-1 5mg-Preservative D 1mg At this time, acetic acid Alternatively, the pH of this coating solution was adjusted to 6.0 using a small amount of sodium hydroxide. Coating amount is 1m on each side
It was 12.4 ml per ² .

[0175]

[Chemical 14]

(Preparation Method of Emulsion O Layer Coating Solution) Each material was added to the emulsion in the following coating amounts. The amount of material applied was 1 m ^{2 on} one side.・ Coated silver amount 0.90 g ・ Gelatin 0.85 g ・ Dextran (average molecular weight 39,000) 214 mg ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 20 mg ・ A-2 102 mg ・ A-3 1.1 mg ・ A- 4 0.25 mg A-5 1.4 mg 1,2-bis (vinylsulfonylacetamido) ethane 25 mg At this time, the coating liquid amount of this emulsion layer was ² per 1 m ² on one side.
It was 2.6 ml.

(Preparation Method of Emulsion U Layer Coating Solution) Each compound was added to the emulsion in the following coating amounts. One side 1m ²
Material coating amount per unit-Coating silver amount 0.35 g-Gelatin 0.40 g-Dextran (average molecular weight 39,000) 130 mg-Sodium polystyrene sulfonate (average molecular weight 600,000) 7 mg-A-2 60 mg-A-30 80 mg A-4 0.10 mg A-5 0.48 mg Dye-1 (oil emulsion) Dye solid content 0.33 g 1,2-bis (vinylsulfonylacetamide) ethane 25 mg At this time, this emulsion layer The amount of coating liquid is 1 per 1 m ² on one side
It was 0.0 ml. The compounds in the above were as follows:

[0178]

[Chemical 15]

(Preparation Method of Surface Protective Layer Coating Solution) Each compound was added so that the coating amount was as follows. Material application amount per 1 m ^{2 on} one side ・ Gelatin 0.767 g ・ Sodium polyacrylate (average molecular weight 400,000) 80 mg ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.1 mg ・ Mat agent-1 (average particle size 3. 7 μm) 70 mg as solid content-A-6 18.1 mg-A-7 34.5 mg-A-8 6.8 mg-A-9 3.2 mg-A-10 1.4 mg-A-11 2.1 mg-A -12 1.0 mg Preservative D 0.9 mg p-benzoquinone 0.7 mg At this time, the pH of the surface protective layer coating solution was adjusted to 6.8 by using a small amount of sodium hydroxide. Coating amount is 1m on each side
It was 10.7 ml per ² . The compounds in the above were as follows.

[0180]

[Chemical 16]

[0181]

[Chemical 17]

[0182]

[Chemical 18]

Corona discharge was performed on a biaxially stretched blue dyeing (containing 1,4-bis (2,6-diethylanilinoanthraquinone) polyethylene terephthalate support having a thickness of 175 μm, and the following main components were added. Each of the coating solutions contained was applied to both sides of the support by a wire bar coater in the order of the first undercoat layer and the second undercoat layer.

First Undercoat Layer (Support Side) The amount of coating solution per 1 m ² on one side of the support was 4.9 ml. The coating amount of each additive material per 1 m ² on one side of the support is as follows. -Styrene-butadiene copolymer latex (as solid content) 0.31 g-Sodium 2,4-dichloro-6-hydroxy-s-triazine 8 mg Drying temperature 190 ° C

The amount of coating liquid per 1 m ² on one side of the second undercoat layer support was 7.9 ml. The coating amount of each additive material per 1 m ² on one side of the support is as follows.・ Gelatin 80 mg ・ C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 1.8 mg ・ Preservative D 0.27 mg ・ Polymethylmethacrylate matting agent having an average particle size of 2.5 μm 2.5 mg Drying temperature 185 ° C.

(Coating method of photographic material) A dye layer is formed from the support side on the undercoated support prepared as described above.
The emulsion U layer, the emulsion O layer, and the surface protective layer were simultaneously coated on both sides by the simultaneous extrusion method so as to have a constitution and dried.

(Measurement of swelling ratio of photographic material) First, the photographic material to be measured was aged for 7 days under the conditions of 40 ° C. and relative humidity of 60%. Next, this sensitive material was immersed in distilled water at 21 ° C. for 3 minutes, and this state was frozen and fixed with liquid nitrogen. This photographic material was cut with a microtome so that its cross section was perpendicular to the surface of the photographic material, and then freeze-dried at -90 ° C. The swelled film thickness Tw was obtained by observing the above-mentioned processed material with a scanning electron microscope. On the other hand, the film thickness Td in the dry state was also obtained by observing the cross section using a scanning electron microscope. Tw obtained in this way
The difference between Td and Td was divided by Td and multiplied by 100 to give a swelling ratio (unit:%). When each photographic material was measured by this method, the swelling ratio was 170%.

(Evaluation of Photographic Performance) The photographic material was brought into close contact with both sides by using an X-ray orthoscreen HGM2 manufactured by Fuji Film Co., Ltd., exposed from both sides for 0.05 seconds, and X-ray sensitive. Totometry was performed. The X-ray apparatus used was a trade name DRX-3724HD manufactured by Toshiba Corporation, and a tungsten target was used. A voltage of 80 kVp was applied to the three phases with a pulse generator, and an X-ray that passed through a filter of 7 cm of water having absorption almost equivalent to the human body was used as a light source. The X-ray exposure amount was changed by the distance method, and logE = 0.
Step exposure was performed with a width of 15. After exposure, development processing was performed under the following development processing conditions, and the density was measured with visible light to obtain a characteristic curve.

(Processing) Automatic developing machine: CEPROS manufactured by FUJIFILM Corporation
-30 Preparation of concentrated solution

[0190] <Developer>   Parts agent A     330 g potassium hydroxide     Potassium sulfite 630 g     Sodium sulfite 255 g     90 g potassium carbonate     Boric acid 45 g     180 g of diethylene glycol     Diethylenetriamine pentaacetic acid 30 g     1- (N, N-diethylamine) ethyl-5-mercapto       Tetrazole 0.75 g     Hydroquinone 450 g     4-hydroxymethyl-4-methyl-1-phenyl-3-       Pyrazolidone 60 g     Add water 4125 ml   Parts agent B     Diethylene glycol 525 g     3,3 'dithiobishydrocinnamic acid 3 g     Glacial acetic acid 102.6 g     2-nitroindazole 3.75 g     1-phenyl-3-pyrazolidone 34.5 g     Add water 750 ml   Parts agent C     Glutaraldehyde (50wt / wt%) 150 g     Potassium bromide 15 g     Potassium metabisulfite 105 g     Add water 750 ml

[0191] <Fixer>     Ammonium thiosulfate (70 wt / vol%) 3000 ml     Ethylenediaminetetraacetic acid / disodium / dihydrate 0.45 g     225 g of sodium sulfite     Boric acid 60 g     1- (N, N-diethylamine) -ethyl-5-mercap       Totetrazole 15 g     Tartaric acid 48 g     Glacial acetic acid 675 g     225 g of sodium hydroxide     Sulfuric acid (36N) 58.5 g     Aluminum sulfate 150 g     6000 ml with the addition of water     pH 4.68

(Preparation of Processing Solution) The developer concentration solution was filled in the processing agent container for CEPRO-30 for each part agent. In this container, the partial containers of the parts agents A, B and C are connected together by the container itself.

Further, the above fixing solution concentration was filled in the same kind of container.

First, 300 m of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was used as a starter in the developing tank.
1 was added.

The processing agent-containing container was turned upside down and inserted into the perforating blade of the processing solution stock tank mounted on the side of the developing machine to break the sealing film of the cap and remove each processing agent in the container. The stock tank was filled.

The developing agent and the fixing tank of the developing machine were filled with the respective processing agents at the following ratios by operating the pumps installed in the developing machine.

Also, every time 8 sheets of photosensitive material were processed in terms of 4-cut size, the stock solution of processing agent and water were mixed at this ratio and replenished in the processing tank of the developing machine.

[0198] Developer Parts agent A 51 ml Parts agent B 10 ml Parts agent C 10 ml 125 ml of water pH 10.50 Fixer Concentrated liquid 80 ml 120 ml of water pH 4.62   The wash tank was filled with tap water.

As a water stain preventive agent, 0.4 g of actinomycetes supported on perlite having an average particle size of 100 μm and an average pore size of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. Prepare three pieces filled with water and fungi from the cloth), two of them at the bottom of the washing tank, and one at the bottom of the stock tank for washing water (liquid volume 0.2 liters). I sunk each.

(Evaluation of Sensitivity) Sensitivity is Fog +
It was expressed by the reciprocal of the exposure amount giving a density of 1.0, and the sensitivity of Sample 1 was 100.

(Evaluation of Residual Color) The photosensitive material was 30.5 cm ×
Cut to 25.4 cm, wash water at 5 ° C and dry
The above-mentioned treatment was performed for 30 seconds in dry, and the degree of residual color of the light-sensitive material was visually evaluated according to the following criteria. A: Almost no color remains. ◯: There is a slight residual color, but it does not bother me. Δ: Color remains, but is practically acceptable. X: Many residual colors are not possible. The results are shown in Table 2.

[0202]

[Table 2]

From Table 2, it can be seen that the silver halide emulsion of the present invention and the light-sensitive material of the present invention using the silver halide emulsion are excellent in sensitivity, Dmax and residual color. For example, in a comparative emulsion having an aspect ratio of 6.9, desensitization is caused by adding the compound of the present invention. Emulsions A to C of the present invention have low sensitivity and high fog in the samples to which the compound of the present invention is not added. On the other hand, by adding the compound of the present invention after the desalting step, the sensitivity and fog are reduced. Further, by increasing the amount of the sensitizing dye IV-1, the sensitization and the fog are reduced, but the residual color is destroyed, and the effect is not exhibited by adding the compound of the present invention during the preparation of the emulsion layer coating solution. Therefore, it is apparent that the present invention can provide a sample having high sensitivity, low fog, and excellent residual color.

[0204]

According to the present invention, high sensitivity and high density (high D
and a silver halide photographic light-sensitive material suitable for rapid processing with less residual color can be obtained.

Claims (2)

[Claims] 1. A silver halide emulsion grain having an average aspect ratio of 8 or more, and the following general formulas (I), (II) and / or (II) after the desalting step in the preparation of the emulsion grain.
A photosensitive silver halide emulsion characterized in that the compound of I) is added. [Chemical 1] (In the formula, R ₁ represents an alkyl group, an alkenyl group or an aralkyl group, and R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a substituent. R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ ,
R ₅ and R ₆ may be condensed. However, R ₂ , R ₃ , R
_At least one of ₄ , R ₅ and R ₆ represents an aryl group.
X ^- represents a counter anion. ) [Chemical 2] (In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent a non-metal atom for completing the nitrogen-containing heterocycle, which may be the same or different. B is a divalent linking group. Represent
m represents 0 or 1. R ₇ and R ₈ each represent an alkyl group. X ^- represents an anion. n represents 0, 1 or 2, and when it is an intramolecular salt, n is 0 or 1. ) 2. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the average aspect ratio of silver halide emulsion grains in the light-sensitive silver halide emulsion layer is A halogen having a number of 8 or more, and the compound of the general formula (I), (II) and / or (III) according to claim 1 is added after the desalting step at the time of preparing the emulsion grains. Silver halide photographic light-sensitive material.