JPH06110146A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material which has a high sensitivity, high contrast and high Dmax and with which images having less black pots are formable. CONSTITUTION:The photosensitive silver halide particles of the silver halide photographic sensitive material contg. a hydrazine deriv. or tetrazolium compd. contains at least one kinds of rhodium, ruthenium, osmium and iridium and have the structure of a core, intermediate phase and the outermost phase. Further, the content of the metal of the intermediate phase is lower than the content thereof in both of the core and the outermost phase.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material used in the field of photoengraving for rapidly forming an ultrahigh contrast image with a highly stable processing solution. It is a thing.

[0002]

2. Description of the Related Art In the field of photoengraving, in order to deal with the variety and complexity of printed matter, there are demands for a photographic light-sensitive material having good original reproducibility, a stable processing solution, and easy replenishment. is there. Especially in the line drawing process, the manuscript is created by pasting phototyped characters, handwritten characters, illustrations, and half-tone dots. Therefore, an image having different densities and line widths is mixed in the original document, and there is a strong demand for a plate-making camera, a photographic light-sensitive material, or an image forming method for finishing these original documents with good reproduction. On the other hand, for catalogs and plate making of large posters, enlarge halftone photographs (expand)
Alternatively, reduction (meshing) is widely performed, and in plate making in which halftone dots are enlarged and used, the number of lines becomes rough, and blurred points are photographed. In reduction, the number of lines / inch is larger than that of the original, and the image is taken at a thin point. Therefore, an image forming method having a wider latitude is required to maintain the reproducibility of halftone. As a system that meets the demand of a wide latitude, a lith-type silver halide light-sensitive material made of silver chlorobromide (at least a silver chloride content of 50% or more) has an extremely low effective concentration of sulfite ion (usually 0.1 mol / mol).
There is known a method of obtaining a line image or a halftone dot image having a high contrast and a high blackening density in which an image area and a non-image area are clearly distinguished by processing with a hydroquinone developer. However, with this method, the concentration of sulfurous acid in the developer is low, so development is extremely unstable against air oxidation, and various efforts and efforts have been made to maintain stable solution activity. However, the current situation is that the work efficiency is reduced due to the extremely slow speed.

For this reason, the instability of image formation due to the above-described developing method (lith development system) is eliminated, and the image is developed with a processing solution having good storage stability to obtain an image having super-high contrast photographic characteristics. A forming system is desired, one of which is US Pat. Nos. 4,166,742 and 4,168,9.
77, 4,221,857, 4,224,40
1, No. 4,243,739, No. 4,272,606
No. 4,311,781, a surface latent image type silver halide photographic light-sensitive material containing a specific hydrazine compound is added at a pH of 11.0 to 12.3 with a sulfurous acid preservative of 0.15. A system has been proposed which forms a super-high contrast negative image having a γ of more than 10 when treated with a developer having a good storage stability of more than 1 mol / liter. The above image system shows excellent performance in terms of sharp halftone dot quality, processing stability, quickness and original reproducibility, but it is more stable and improved in original reproducibility in order to cope with the recent variety of printed matter. An optimized system is desired.

One of the points to be improved in this new high contrast negative image system is black spots.
This is an unfavorable development, which is a problem in the photomechanical process. A black spot is a black spot made of minute developed silver that originally occurs in a portion that should be a non-image when it is not exposed. Black spots frequently occur due to a decrease in sulfite ion, which is generally used as a preservative in a developing solution, and an increase in pH value, and the commercial value as a photosensitive material for photoengraving is remarkably reduced. For this reason, great efforts have been made to improve the black spots, but the black spot improvement is often accompanied by a decrease in sensitivity and gamma (γ) while maintaining a high sensitivity (for example, γ of 10 or more). A system for improving black spots has been strongly desired.

On the other hand, a halogen lamp or a xenon lamp is used as the light source of the plate making camera. In order to obtain photographing sensitivity for these light sources, the photographic light-sensitive material is usually ortho-sensitized. However, it has been found that the ortho-sensitized photographic light-sensitive material is more strongly affected by the chromatic aberration of the lens, so that the image quality is likely to deteriorate. Further, this deterioration becomes more remarkable for the xenon lamp light source. In addition to the above, in order to cope with the recent variety of printed matter, a system having improved original reproducibility has been desired in the image system.

In addition to the system using the hydrazine compound described above, JP-B-59 is one of the image systems capable of eliminating the instability of image formation by the lith development system described above and obtaining super-hard photographic characteristics. -17825, 5
Each publication such as 9-17826 discloses a silver halide photographic light-sensitive material containing a tetrazolium compound. This image forming system has a problem that it is difficult to reduce fog. Therefore, an organic compound called a so-called antifoggant is added to improve fog, but this is often accompanied by a decrease in sensitivity and gamma (γ). Therefore, even in this system, it has been strongly desired to maintain high sensitivity and high contrast (for example, γ is 10 or more) and obtain photographic characteristics with low fog.

An example in which a silver halide grain containing a Group VIII metal and a hydrazine derivative are used in combination is disclosed in JP-A-61-2.
9837, 61-47942, 63-2960.
No. 31, etc. In addition, VIII in the particles
Japanese Patent Application Laid-Open No. 63-296031 discloses an example in which a silver halide grain characterized by the distribution of a group metal and a hydrazine derivative are used in combination.
JP-A-2-306236 and JP-A-3-167545.
No. 4-76534 and the like.

It comprises a core, an intermediate phase and an outermost phase, and contains at least one of rhodium, rhenium, ruthenium and osmium.
In the seed-containing silver halide grain, an example of the silver halide grain characterized by containing at least one intermediate phase having a lower content of the metal than the core and the outermost phase is,
Although it is described in Japanese Patent Application No. 4-68304, there is no example in which it is used in combination with a hydrazine derivative or a tetrazolium compound.

Examples of a system using hydrazine containing a redox compound which releases a development inhibitor upon being oxidized are disclosed in JP-A-61-213847 and 64-7214.
No. 0 and the like.

[0010]

The first object of the present invention is to provide high sensitivity, high contrast (for example, γ of 10 or more),
An object of the present invention is to provide a silver halide photographic light-sensitive material which maintains a high Dmax and has a good black spot, or a silver halide photographic light-sensitive material which has low fog. A second object of the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity, high contrast, high Dmax, good black spot and good original reproducibility.

[0011]

The first object of the present invention is to:
A silver halide photographic light-sensitive material having at least one photosensitive emulsion layer containing silver halide grains containing at least one of rhodium, rhenium, ruthenium, osmium and iridium on a support, the silver halide grains being the core. , An intermediate phase, an outermost phase, at least one intermediate phase having a core and a lower content of the metal than the outermost phase, and a hydrazine derivative or a tetrazolium compound in the emulsion layer or other hydrophilic colloid layer. And a silver halide photographic light-sensitive material. The second object of the present invention has been achieved by a silver halide photographic light-sensitive material containing a redox compound which releases a development inhibitor when oxidized to the above silver halide photographic light-sensitive material containing a hydrazine derivative.

The specific constitution of the present invention will be described in detail below. The halogen composition of the silver halide emulsion used in the present invention includes silver chloride, silver chlorobromide, silver iodochlorobromide, silver bromide,
Any composition such as silver iodobromide may be used without particular limitation, but the silver chloride content is 30 mol% or more, more preferably 50 mol%.
Above all, either silver chlorobromide or silver iodochlorobromide is preferable. The silver iodide content is 3 mol% or less, more preferably 0.
It is 5 mol% or less. Further, it may have a so-called core / shell structure in which the inside and the surface layer have different halogen compositions.

The particles of the present invention may have a regular crystal such as cubic particles, tetradecahedral particles or octahedral particles, and also irregular particles such as spheres and plates. with (irregular) crystals, or
Although it may have a composite form of these crystal forms,
Those having regular crystals are preferable, and cubic particles are particularly preferable.

The average grain size of the silver halide emulsion in the present invention is preferably 0.5 μm or less, more preferably 0.1 μm to 0.4 μm. The particle size distribution is preferably monodisperse. The monodisperse grain as used herein means a silver halide emulsion having a grain size distribution having a coefficient of variation of 20% or less, particularly preferably 15% or less. The variation coefficient (%) here is the value obtained by dividing the standard deviation of the particle diameter by the average value of the particle diameter by 100.

The silver halide grains used in the present invention are described in P.
Chemie et Physique Photographique (Pau by Glafkides
l Montel, 1967), GF Duffin Photog
raphic Emulsion Chemistry (The Focal Press, 1
966), by VL Zelikman et al Making and Coati
ng Photographic Emulsion (The Focal Press, 19
64) 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 and a combination thereof may be used. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used.

As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.
Further, in order to make the particle size uniform, US Pat.
No. 535, 016, Japanese Patent Publication No. 48-36890, No. 52-
16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, British Patent 4,242,445, and JP-A-55-55.
As described in JP-A-158124, it is preferable to use a method in which the concentration of the aqueous solution is changed and to grow it quickly in a range not exceeding the critical saturation.

The grain formation of the silver halide emulsion of the present invention comprises
It is preferably carried out in the presence of a silver halide solvent such as a tetra-substituted thiourea or an organic thioether compound. Preferred tetra-substituted thiourea silver halide solvents used in the present invention are
The compounds are described in JP-A Nos. 53-82408 and 55-77737. A preferred organic thioether silver halide solvent used in the present invention is, for example, JP-B-47.
No. -11386 (U.S. Pat. No. 3,574,628) compounds comprising at least one of the recited oxygen atom and group the sulfur atom are separated by an ethylene (e.g. -O-CH ₂ CH ₂ -S-) in such JP-A-54-155828 (U.S. Pat. No. 4,276,374), wherein an alkyl group at both ends (wherein each alkyl group is at least 2 selected from hydroxy, amino, carboxy, amido or sulfone).
It is a chain thioether compound having one substituent).

The amount of silver halide solvent added depends on the compound used.
Type of product, target particle size, halogen composition
10 per mol of silver halide, depending on which one^-Five~
10 ^-2Molar is preferred. By using a silver halide solvent
If the particle size is larger than intended, the temperature during particle formation
Degree, silver salt solution, halogen salt solution addition time, etc.
By doing so, a desired particle size can be obtained.

The silver halide grains used in the present invention are
It consists of a core, at least one intermediate phase, and an outermost phase. The halogen compositions of the core, the intermediate phase, and the outermost phase may be the same or different, but they are distinguished by the difference in the doping ratio of the metal selected from rhodium, rhenium, ruthenium, osmium, and iridium. The core and the outermost phase contain at least one metal selected from rhodium, rhenium, ruthenium, osmium, and iridium. This content is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol with respect to 1 mol of silver (forming the phase),
Furthermore, the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol is preferable. Two or more of these metals may be used in combination. The intermediate phase is composed of at least one phase and may have a plurality of phases.
The intermediate phase may or may not contain the above-mentioned three kinds of metals, but has at least one phase having a content ratio smaller than that of either the core or the outermost phase. The ratio is 0 to 0.
7 is preferable, and 0 to 0.3 is more preferable. The volume ratio of the core, the intermediate phase, and the outermost phase is arbitrary, but the outermost phase is advantageously 1/3 or less, and more preferably 1/100 to 1/10. The ratio of the core and the intermediate phase is preferably in the range of 1/5 to 5/1, but it is essentially arbitrary. Rhodium, rhenium, ruthenium, osmium, and iridium are disclosed in JP-A-6-6
No. 3-2042, Japanese Patent Laid-Open No. 1-285941, Japanese Patent Laid-Open No.
It is added in the form of a water-soluble complex salt described in JP-A-20852 and JP-A-2-20855. Particularly preferred is a hexacoordinated complex represented by the following formula 1.

[0020]

[Equation 1]

In this case, the counterion has no significance and ammonium or alkali metal ions are used.
Examples of preferable ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl and thionitrosyl ligands. Examples of specific complexes used in the present invention are shown.

[0022]

[Chemical 1]

[0023]

[Chemical 2]

In order to add these compounds to the silver halide grains by adding them during the grain formation of the silver halide, a powder of the metal complex or an aqueous solution or an aqueous solution dissolved with NaCl or KCl is used to form the grains. A silver halide grain is prepared by a method of adding it to a water-soluble silver salt or a water-soluble halide solution, or as a third solution when a silver salt and a halide solution are simultaneously mixed, and a three-liquid simultaneous mixing method. Or a method in which a necessary amount of an aqueous solution of a metal complex is charged into a reaction vessel during the formation of particles. Particularly preferred is a method of adding powder or an aqueous solution dissolved together with NaCl and KCl to the water-soluble halide solution. To add to the surface of the particles, a necessary amount of an aqueous solution of the metal complex may be added to the reaction vessel immediately after the particles are formed, during or during physical ripening, or at the time of chemical ripening. Also,
It is also possible to add the silver halide emulsion at a stage before coating. The silver halide grain in the present invention may be doped with another heavy metal salt. Especially K ₄ [Fe (C
N) ₆ ] is preferably used to dope the Fe salt.

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

The sulfur sensitization used in the present invention is usually a sulfur sensitization.
Add a yellow sensitizer and keep the emulsion at a high temperature of 40 ℃ or more
It is performed by stirring for a while. Public as a sulfur sensitizer
Known compounds can be used, eg in gelatin
In addition to the sulfur compounds contained in
For example, thiosulfates, thioureas, thiazoles, rhodani
And the like can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. Addition of sulfur sensitizer
The amount depends on the pH, temperature, and large amount of silver halide grains during chemical ripening.
Silver halide, although it changes under various conditions such as texture
10 per mole ^-7-10^-2Mol, more preferably
10^-Five-10^-3It is a mole.

Known selenium compounds can be used as the selenium sensitizer used in the present invention. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
The compounds described in No. 121798 and the like can be used. Especially, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compounds represented by and (IX).

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to serve as a sensitizing nucleus, on the surface or inside of the silver halide grain. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, Journal of Chemical Society Chemical Communication
(J. Chem. Soc. Chem. Commun.) 635 (1980),
ibid 1102 (1979), ibid 645 (197)
9), Journal of Chemical Society
Perkin Transaction (J. Chem. Soc. Perkin. T
rans.) 1,191 (1980), S. Patai
Hen, The Chemistry of Organic Selenium and Tellurium Companies (The Chemistry
of Organic Serenium and Tellunium Compounds), Vol
1 (1986) and the same Vol 2 (1987) can be used. Particularly preferred are the compounds represented by the general formulas (II) (III) (IV) in Japanese Patent Application No. 4-146739.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions, etc., but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide. About 10 ^-7 to 10 ^-2 mol per mol of silver halide is used. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of formation of silver halide grains or physical ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. The silver halide emulsion of the present invention can be prepared by the method disclosed in European Patent Publication (EP) -293,917.
A thiosulfonic acid compound may be added. The silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, chemically sensitized ones). Different conditions) may be used together.

Next, the hydrazine derivative used in the present invention will be described. The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (A). General formula (A)

[0033]

[Chemical 3]

In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ₁ represents- CO- group, -SO ₂ - group, -S
O- _{group, -P (O) (R 2} ) - represents group, -CO-CO- group, a thiocarbonyl group or an iminomethylene group, A _1, A
Both ₂ represent a hydrogen atom or a hydrogen atom in one and a substituted or unsubstituted alkylsulfonyl group in the other, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (A), the aliphatic group represented by R ₁ is preferably one having 1 to 30 carbon atoms, and particularly a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. is there. This alkyl group may have a substituent.
The aromatic group represented by R ₁ in the general formula (A) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be condensed with an aryl group. Preferred as R ₁ is an aryl group, and particularly preferred is one containing a benzene ring.

The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group and a substituted amino group. , Ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group , Acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoramide group, diacylamino group, imide group, R ₂ -NH
—CO—N (R ₂ ) —CO— group and the like can be mentioned, and a preferable substituent is an alkyl group (preferably having 1 to 20 carbon atoms).
, An aralkyl group (preferably having a carbon number of 7 to 30), an alkoxy group (preferably having a carbon number of 1 to 20), a substituted amino group (preferably an alkyl group having a carbon number of 1 to 20) Amino group), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), And a phosphoric acid amide group (preferably having a carbon number of 1 to 30).

The alkyl group represented by R ₂ in the general formula (A) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, a benzene ring). Including). G ₁
Is a —CO— group, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (for example, a methyl group,
Trifluoromethyl group, 3-hydroxypropyl group, 3
-Methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (for example, o-hydroxybenzyl group, etc.), aryl group (for example, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group,
2-hydroxymethylphenyl group) and the like, and a hydrogen atom is particularly preferable.

R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied. Most preferably, G _{1 in the} general formula (A) is a —CO— group.
R ₂ also splits the G ₁ -R ₂ part from the rest of the molecule,
It may be one that causes a cyclization reaction to form a cyclic structure containing an atom of the -G ₁ -R ₂ moiety, and examples thereof include those described in JP-A-63-29751. Can be mentioned. A hydrogen atom is most preferable as A ₁ and A ₂ .

R ₁ or R _{2 in} the general formula (A) may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-1005
Those described in No. 30 are mentioned.

R ₁ or R _{2 in} the general formula (A) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include U.S. Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
4,459,347, JP-A-59-195,233.
No. 59-200, 231, 59-201, 04
No. 5, No. 59-201, 046, No. 59-201, 0
No. 47, No. 59-201, No. 048, No. 59-201,
049, JP-A-61-170, 733 and 61-2.
70,744, 62-948, 63-2342.
No.44, No.63-234245, No.63-23424
The groups described in No. 6 are mentioned. Specific examples of the compound represented by formula (A) are shown below. However, the present invention is not limited to the following compounds.

[0041]

[Chemical 4]

[0042]

[Chemical 5]

[0043]

[Chemical 6]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,207.
No. 4,169,929, 4,276,364
Nos. 4,278,748, 4,385,108
Nos. 4,459,347 and 4,560,638
No. 4,478,928, British Patent No. 2,011,3
91B, JP-A-2-12236, and JP-A-3-174143.
It is possible to use those described in No. The addition amount of the hydrazine derivative in the present invention is silver halide 1
It is preferably contained in an amount of 1 × 10 ^-6 to 5 × 10 ^-2 mol, particularly 1 × 10 ^-5 to 2 × 10 5.
^The preferable addition amount is ^-2 mol.

Next, the tetrazolium compound used in the present invention will be described. A preferable tetrazolium compound is represented by the following general formula (T). General formula (T)

[0046]

[Chemical 7]

In the above general formula (T), R _{1 to} R ₃ are alkyl groups (for example, methyl, ethyl, cyclopropyl,
Propyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), amino group, acylamino group (eg acetylamino), hydroxyl group, alkoxy group (eg methoxy, ethoxy, propoxy, butoxy, pentoxy), acyloxy group ( For example, acetyloxy), halogen atom (eg fluorine, chlorine, bromine), carbamoyl group, acylthio group (eg acetylthio), alkoxycarbonyl group (eg ethoxycarbonyl), carboxyl group, acyl group (eg acetyl), cyano group, nitro group , A mercapto group, a sulfooxy group, and an aminosulfooxy group.

The X ⁻ represents an anion. Preferably,
For example, halogen ions such as chloride ions, bromide ions, and iodide ions, acid radicals of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, acid radicals of organic acids such as sulfonic acids and carboxylic acids, anionic activators, concrete Are higher alkyl sulfate ester anions such as p-toluenesulfonate anion, p-dodecylbenzenesulfonate anion, and lauryl sulfate anion; borate anions such as tetraphenylboron; and dialkylsulfones such as di-2-ethylhexylsulfosuccinate. Examples thereof include polyether alcohol sulfate anions such as succinate anion and cetyl polyethenoxysulfate anion, higher fatty acid anions such as stearic acid anion, and polymers having acid radicals such as polyacrylic acid anion. Specific examples of the compound represented by formula (T) used in the present invention are shown in Table 1 below, but the compound of the present invention is not limited thereto.

[0049]

[Table 1]

The tetrazolium compound used in the present invention is, for example, a chemical review No. 5
It can be easily synthesized by the method described in Volume 5, pages 335 to 483. The tetrazolium compound represented by the general formula (T) of the present invention is contained in the silver halide photographic light-sensitive material of the present invention in an amount of about 1 mg to 10 g, preferably about 10 mg to 2 g per mol of silver halide. It is preferably used in a range. The tetrazolium compound represented by the general formula (T) used in the present invention may be used alone or in combination of two or more kinds at an appropriate ratio. Further, the tetrazolium compound of the present invention and the tetrazolium compound other than the present invention may be used in combination at an appropriate ratio.

In the present invention, particularly preferable results can be obtained by using an anion which is combined with the tetrazolium compound of the present invention and reduces the hydrophilicity of the tetrazolium compound of the present invention. Examples of such anions include acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically lower alkylbenzene such as p-toluenesulfonic acid anion. Sulfonate anion, p-dodecylbenzene sulfonate anion, alkylnaphthalene sulfonate anion, lauryl sulfate anion, tetraphenylboron, di-2-ethylhexyl sulfosuccinate anion, etc., dialkyl sulfosuccinate anion, cetyl polyanion Examples thereof include polyether alcohol sulfate anion such as ethenoxysulfate anion, stearic acid anion, and polyacrylic acid anion. Such anions may be mixed with the tetrazolium compound of the present invention in advance and then added to the hydrophilic colloid layer. Alternatively, the anion alone may contain the tetrazolium compound of the present invention or may not contain the tetrazolium compound or the hydrophilic layer. It can be added to the colloid layer.

In the present invention, it is preferable to use a redox compound which can release a development inhibitor when oxidized. As the redox group of the redox compound, hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones,
Hydrazines, hydroxylamines and reductones are preferable, and hydrazines are more preferable. In addition, it is preferable that at least a part of the development inhibitor is a redox compound that can be eluted into a developer and react with a developer component to be converted into a compound having less inhibitory properties. The hydrazines used as the redox compound capable of releasing the development inhibitor by being oxidized in the present invention are represented by the following general formula (R-1), general formula (R-2) and general formula (R-3). Be done. The compound represented by formula (R-1) is particularly preferable.

[0053]

[Chemical 8]

[0054]

[Chemical 9]

[0055]

[Chemical 10]

In these formulas, R ₁ represents an aliphatic group or an aromatic group. G ₁ is a —CO— group, a —CO—CO— group,
-CS- _{group, -C (NG 2 R 2)} - group, -SO- group, -S
O ₂ - group or a -PO (G ₂ R ₂₎ - represents a group. G ₂ represents a simple bond, —O—, —S— or —NR ₂ —, and R ₂ represents a hydrogen atom or R ₁ . A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ is synonymous with A ₁ or -CH ₂ -CH (A ₄ )-(Time)
Represents _t- PUG. A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G ₁ -G ₂ -R _1.
Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor.

General formulas (R-1), (R-2), (R-
3) will be described in more detail. General formula (R-
In 1), (R-2) and (R-3), the aliphatic group represented by R ₁ is preferably one having 1 to 30 carbon atoms, particularly straight chain or branched one having 1 to 20 carbon atoms. Alternatively, it is a cyclic alkyl group. This alkyl group may have a substituent. In the general formulas (R-1), (R-2) and (R-3), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group. For example, among benzene rings, naphthalene rings, pyridine rings, quinoline rings, isoquinoline rings, etc., those containing a benzene ring are preferable.

Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical examples of the substituent include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl Group, an acyloxy group, a carbonamido group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, etc., and a preferable substituent is a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms). , Aralkyl groups (preferably having 7 to 30 carbon atoms) , An alkoxy group (preferably having 1 to 30 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), an acylamino group (preferably having 2 to 40 carbon atoms) ), A sulfonamide group (preferably having 1 to 4 carbon atoms)
0), ureido group (preferably having 1 to 4 carbon atoms)
Those having 0), phosphoric acid amide groups (preferably having 1 carbon atom)
~ 40) and the like.

General formulas (R-1), (R-2), (R-
As G _{1 in} 3), a —CO— group and a —SO ₂ — group are preferable, and a —CO— group is the most preferable. A ₁ and A ₂ are preferably hydrogen atoms, A ₃ is a hydrogen atom, —CH ₂ —CH
(A ₄ )-(Time) _t -PUG is preferred.

General formulas (R-1), (R-2), (R-
In 3), Time represents a divalent linking group and may have a timing adjusting function. The divalent linking group represented by Time represents a group capable of releasing PUG from Time-PUG released from the oxidized product of the redox mother nucleus through a reaction in one step or more steps.

Examples of the divalent linking group represented by Time include, for example, US Pat.
4-145,135) and the like, which release PUG by an intramolecular ring closure reaction of a p-nitrophenoxy derivative; US Pat. No. 4,310,612 (JP-A-55-5).
U.S. Pat. Nos. 4,330,617 and 4,44, which release PUG by an intramolecular ring closure reaction after ring cleavage described in U.S. Pat.
6,216, 4,483,919, JP-A-59-
No. 4,409,323, which releases PUG with the formation of an acid anhydride by the intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or its analogs described in US Pat. No. 4,409,323; Same as 4,421,845
Issue, Research Disclosure No. 21,228
(December 1981), U.S. Pat. No. 4,416,977.
(JP-A-57-135,944), JP-A-58-2
09,736, 58-209,738, etc. to generate quinomonomethane or an analog thereof by electron transfer through a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG. U.S. Pat. No. 4,420,554 (JP-A-57-136,640)
No. 57,135,945, 57-18.
8,035, 58-98,728 and 58-
209,737 and the like, which releases PUG from the γ-position of the enamine by electron transfer of the portion having the enamine structure of the nitrogen-containing heterocycle described in JP-A-57-56,837. Release of PUG by intramolecular ring closure reaction of oxy group formed by electron transfer to carbonyl group conjugated with nitrogen atom; US Pat. No. 4,14
6,396 (JP-A-52-90932), JP-A-5
No. 9-93,442, JP-A-59-75475, JP-A-60-249148, JP-A-60-249149, etc., which release PUG with formation of aldehydes; 51-146,828, ibid. 57-17
Those releasing PUG with decarboxylation of the carboxyl group described in Nos. 9,842 and 59-104,641;
O-COOCR _a R _b -PUG (R _a and R _b represent a monovalent group) and releases PUG with decarboxylation and subsequent formation of aldehydes; -7,
429 with formation of the isocyanate described in No. 429
Examples thereof include those that release PUG by a coupling reaction with an oxidant of a color developing agent described in US Pat. No. 4,438,193 and the like. Specific examples of these divalent linking groups represented by Time are described in JP-A Nos. 61-236,549 and 1-26.
It is also described in detail in Japanese Patent Application No. 9,936, Japanese Patent Application No. 2-93,487 and the like.

PUG is (Time) _t -PUG or P
UG represents a group having a development inhibiting effect. PUG
Is preferably a development inhibitor capable of reacting with the components of the developer and converting into a compound having less inhibitory properties when flowing out to the developer. Development inhibitors represented by PUG or (Time) _t -PUG are known development inhibitors which have a heteroatom and are attached via a heteroatom, these are, for example, CEKMess. ) And TH James, "The Theory
The Theory Process
of the Photographic Processes) "3rd edition, 1967
, Pp. 344-346, published by Macmillan.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include those enumerated as the substituents of R ₁ , and these groups may be further substituted. Preferred substituents are nitro group, sulfo group, carboxyl group, sulfamoyl group, phosphono group, phosphinico group and sulfonamide group.

The general formulas (R-1), (R-2) and (R
In -3), R ₁ or-(Time) _t -PUG is a ballast group or a general formula (R-1) or (R-2) commonly used in a non-moving photographic additive such as a coupler. , (R
A group which promotes adsorption of the compound represented by -3) to silver halide may be incorporated. The ballast group is an organic compound giving a molecular weight sufficient to prevent the compounds represented by the general formulas (R-1), (R-2) and (R-3) from substantially diffusing into another layer or the treatment liquid. The base,
It is composed of a combination of one or more of an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, an amide group, a ureido group, a urethane group and a sulfonamide group. The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the adsorption promoting group for silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine,
Thiobarbituric acid, tetrazoline-5-thione, 1,
2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzthiazoline-2-thione, thiotriazine, 1,3- Cyclic thioamide group such as imidazoline-2-thione, chain thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (if the carbon atom to which the -SH group is bonded is adjacent to a nitrogen atom, it is bound to this It has the same meaning as the cyclic thioamide group in the relationship of variants, and specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benzimidazole. , Imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oxa Group, a 5-membered to 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur and carbon such as benzene, oxazoline, thiadiazole, oxathiazole, triazine and azaindene, and a heterocyclic tetracyclic group such as benzimidazolinium. Examples include graded salts.

These may be further substituted with appropriate substituents. Examples of the substituent include those mentioned as the substituent of R ₁ . Specific examples of the compound used in the present invention are listed below, but the present invention is not limited thereto.

[0067]

[Chemical 11]

[0068]

[Chemical 12]

[0069]

[Chemical 13]

[0070]

[Chemical 14]

As the redox compound used in the present invention, in addition to the above-mentioned ones, for example, JP-A-2-301743.
Of the compounds represented by formula (I) in the publication (particularly compound examples 1 to 50) and the compounds represented by formulas (R-1), (R-2) and (R-3) described in the publication 3-174143. Compound Examples 1 to 75, and Japanese Patent Application Nos. 3-69466 and 3-15
The compounds described in No. 648 can be used. The method for synthesizing the redox compound used in the present invention is described in, for example, JP-A Nos. 61-213,847 and 62-260,153,
U.S. Pat. No. 4,684,604, Japanese Patent Application No. 63-98,
803, U.S. Pat. Nos. 3,379,529 and 3,6.
20,746, 4,377,634, 4,33
2,878, JP-A-49-129,536 and 56.
No. 153,336, No. 56-153,342.

The redox compound of the present invention is used within the range of 1 × 10 ^{-6 to} 5 × 10 ^-2 mol, and more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver halide. . The redox compound of the present invention is suitable for use in a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. It can be dissolved and used. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, by a method known as a solid dispersion method, the powder of the redox compound is ball milled in water, a colloid mill,
Alternatively, they can be dispersed by ultrasonic waves and used.

The layer containing the redox compound of the present invention may contain silver halide emulsion grains and / or a hydrazine derivative, or may be another hydrophilic colloid layer. As an example in which the photosensitive emulsion layer contains a hydrazine derivative and the other hydrophilic colloid layers contain the redox compound of the present invention, Japanese Patent Application Nos. 1-108215 and 1-
There are 240967 and the like. At this time, the layer containing the redox compound of the present invention may be either the upper layer or the lower layer of the photosensitive emulsion layer containing the hydrazine nucleating agent. The layer containing the redox compound of the present invention may further contain light-sensitive or light-insensitive silver halide emulsion grains. An intermediate layer containing gelatin or a synthetic polymer (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided between the layer containing the redox compound of the present invention and the photosensitive emulsion layer containing the hydrazine nucleating agent.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention and the development processing method. For example, those described in the following sections can be preferably used. Item Relevant part 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 Spectral sensitization described on page 17, lower left column, line 20, and further in JP-A Nos. 1-112235, 2-124560, 3-79928, Japanese Patent Application Nos. 3-189532 and 3-41, 1064. Pigment. 2) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to page 4, Lower right column, line 18. 3) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A-1-237538 The thiosulfinic acid compound described in the official gazette. 4) Polymer Latte JP-A-2-103536, page 18, lower left column, line 12 to line 20. 5) Chemical compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to compound, page 19 upper left column, line 1 6) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column, line 15 From plasticizer, page 19 upper right column, line 15

7) Dyes: Dyes from JP-A-2-103536, page 17, lower right column, lines 1 to 18; solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-187573. . 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Nucleation accelerators JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II-p) and compound example II -1 to II-22, compounds described in JP-A-1-179939. 10) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 11) Monomethine compound A compound of the general formula (II) described in JP-A-2-287532 (in particular, compound examples II-1 to II-26). 12) Dihydroxy Compounds described in JP-A-3-39948, page 11, upper left column to benzene 12, benzene, page lower left column, and EP452772A.

In order to obtain ultrahigh contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. Regarding the development processing method of the light-sensitive material of the present invention, JP-A-2-103536, No. 1
Reference can be made to the description from page 9, upper right column, line 16 to page 21, upper left column, line 8 of the same.

[0077]

【Example】

Example 1 An emulsion having a core / mesophase / outermost phase was prepared by the following method. Emulsion-1: Aqueous silver nitrate solution 250 in which 63 g of silver nitrate was dissolved
cc, potassium bromide 18g and sodium chloride 13.5g
250cc of an aqueous solution of halogen salt in which is dissolved in a 2% gelatin aqueous solution containing sodium chloride (0.5%) and 1,3-dimethyl-2-imidazolithione (0.002%) with stirring at 38 ° C for 12 minutes. A core particle having an average particle size of 0.20 μm was prepared by adding by the double jet method. Next, a silver nitrate aqueous solution 35 in which 85 g of silver nitrate is dissolved
0cc, potassium bromide 24g and sodium chloride 18.5
350 cc of a halogen salt aqueous solution in which g was dissolved was added by the double jet method over 16 minutes to obtain core / intermediate phase particles. Furthermore, 100 cc of an aqueous solution of silver nitrate having 22 g of silver nitrate dissolved therein, 6 g of potassium bromide and 4.7 ml of sodium chloride.
100 cc of a halogen salt aqueous solution in which g was dissolved was added by the double jet method over 4 minutes to obtain particles having a core / intermediate phase / outermost phase.

Thereafter, 1 × 10 ⁻³ mol of KI solution was added to 1 mol of silver for conversion, followed by washing with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per 1 mol of silver, pH 6.0, pAg7 Adjusted to 0.5, and further, per mol of silver, 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, and 8 mg of chloroauric acid.
And 5 mg of sodium thiosulfate were added, and the mixture was heated at 60 ° C. for 45 minutes for chemical sensitization, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 150 mg as a stabilizer and a preservative were used. 100 mg of Proxel was added. The obtained particles have an average particle size of 0.27 μm,
The silver iodochlorobromide cubic grains had a silver chloride content of 60 mol%. (Variation coefficient 10%)

The core / intermediate phase / outermost phase will be described below.
Gold contained in the halogen salt solution added during grain formation
Included in core / mesophase / outermost phase by changing the metal complex salt
Prepared silver halide grains with different metal species and amount
It was For example, in Emulsion-2, the halogen salt water used when preparing the core
2.7 × 10 per mol of silver contained in the solution ^-7
K equivalent to the mole₂Rh (H₂O) Cl_FiveAdd halo
Silver genide grains were prepared. The particles obtained are summarized in Table 2.
Showed. After grain formation, KI
It was converted, washed with water and chemically sensitized.

[0080]

[Table 2]

The emulsion thus obtained was added with 4 × 10 ⁻⁴ mol of 5- [3-mol as a sensitizing dye per mol of silver.
(4-Sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt was added, and 4 × 10 ⁻⁴ mol was further added. A short-wave cyanine dye represented by the following structural formula (A), 3 × 10 ⁻⁴ mol of a mercapto compound represented by the following structural formula (B), 4 × 1
0 ^-4 mol of the mercapto compound represented by the following structural formula (C), 4 x 10 ^-4 mol of the triazine compound represented by the following structural formula (D), 2 x 10 ^-3 mol of 5-chloro-8 -Hydroxyquinoline, A- as the hydrazine compound of the present invention
8 × 10 ⁻⁴ mol of ⁴ and 4 × 10 ⁻⁶ mol of A-11 were added, and further N-oleyl-N-methyltaurine sodium salt was added so as to be coated at 30 mg / m ² . Water-soluble latex (200 mg / m ² ) represented by (E)
And polyethyl acrylate dispersion (300 mg /
m ² ) 1,3-Divinylsulfonyl-2-propanol (200 mg / m ² ) was added as a hardening agent. The pH of the solution was adjusted to 6.0. They were coated on an undercoated polyethylene terephthalate film so that the coating silver amount was 3.6 g / m ² .

[0082]

[Chemical 15]

As a protective layer on these emulsion layers, gelatin 1.5 g / m ² , amorphous SiO ₂ matting agent 40 mg / m ² having an average particle size of about 3.5 μ, methanol silica 0.
1 g / m ² , polyacrylamide 50 mg / m ² , hydroquinone 50 mg / m ² and silicone oil, proxel and phenoxyethanol as preservatives, and a fluorosurfactant 5 mg / m ^{2 represented by the following} structural formula (F) as a coating aid. Sodium dodecylbenzene sulfonate 40 mg / m ² was applied to prepare samples 1 to 16 as shown in Table 4. The film surface pH of the obtained sample was 6.0.

[0084]

[Chemical 16]

The back layer was coated according to the following formulation. (Back layer formulation) Gelatin 3.2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 40 mg / m ² Gelatin hardener 1,3-divinylsulfonyl-2 -Propanol 200 mg / m ² dye Mixture of the following dyes (G), (H), (I), (J) Dye (G) 20 mg / m ² Dye (H) 50 mg / m ² Dye (I) 20 mg / m ² dyes (J) 30mg / m ²

[0086]

[Chemical 17]

(Back protective layer) Gelatin 1.3 g / m ² polymethylmethacrylate fine particles (average particle size 2.5 μ) 20 mg / m ² sodium p-dodecylbenzenesulfonate 15 mg / m ² dihexyl-α-sulfosuccinate sodium Salt 15 mg / m ² Sodium acetate 60 mg / m ²

The sample thus obtained was exposed to a tungsten light source through a step wedge and used as a developing solution in Table 3.
GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used as a developing solution and a fixing solution having the formulation shown in 1. and processed using an FG-710F automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.).

[0089]

[Table 3]

The sensitivity is shown by a common logarithmic value of the exposure amount which gives a fog of +1.5 at 34 ° C. for 30 seconds. The value of Sample 1 was set to 1, and the larger the value, the higher the feeling. γ is represented by a value represented by the following mathematical formula. Dmax
Is logE for the sensitivity point of concentration +0.1 on the characteristic curve.
The density is shown at an exposure amount of +0.5. Black spot is 34
The actual portion when developed at 40 ° C. was evaluated on a scale of 5 by microscopic observation. “5” is the best and “1” is the worst quality. "5" or "4" is practical, "3" is poor but practically usable, and "2" or "1" is not practical. The results are shown in Table 4.

[0091]

[Equation 2]

[0092]

[Table 4]

Sample 1-1 using emulsion containing no heavy metal
Black spots are extremely bad. Samples 1-7 and 1 of the constitution of the present invention
It can be seen that −8 has the same γ and Dmax as compared with Sample 1-2 in which the same amount of rhodium is uniformly added in total, and has high sensitivity and good black spots. Moreover, even if compared with Samples 1-3 and 1-4 in which rhodium was added only to the core, and Samples 1-5 and 1-6 in which rhodium was added only to the outermost phase, clearly good black spot performance was shown. . With respect to the samples using other heavy metals, as is clear from Table 4, the samples having the constitution of the present invention showed high sensitivity and good black spots. Although not shown in the table, in the sample to which the hydrazine compound of the present invention was not added, γ was around 7, and γ was insufficient as a photosensitive material for printing plate making.

Example 2 16 kinds of silver halide emulsions prepared by grain formation, washing with water and addition of gelatin in the same manner as in the emulsions 1 to 16 prepared in Example 1 were adjusted to pH 5.9 and pAg 7.3, respectively, to obtain silver. 1
Add 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 5 mg of chloroauric acid, 2 mg of sodium thiosulfate and 2 mg of tellurium sensitizer represented by the following structural formula (M) per mole, and heat at 60 ° C. for 45 minutes to perform chemistry. Sensitized. Thereafter, a stabilizer and a preservative were added in the same manner as in Example 1 to obtain silver halide emulsions 17 to 32.

[0095]

[Chemical 18]

A sensitizing dye and the like were added to the emulsion thus obtained in exactly the same manner as in Example 1 and the emulsion was coated with a protective layer and a back layer to prepare a sample. The film surface pH of the sample was 5.8. The sample thus obtained was evaluated by the same method as in Example 1, and as in Example 1, the sample having the constitution of the present invention showed good performance.

Example 3 In place of adding 2 mg of the tellurium sensitizer represented by the structural formula (M) in Example 2, 1.5 mg of the selenium sensitizer represented by the following structural formula (N) was added. When a sample was prepared and evaluated in exactly the same manner, the sample having the constitution of the present invention showed good performance.

[0098]

[Chemical 19]

Example 4 Emulsions 1 to 16 prepared in Example 1 were each used as a sensitizing dye in an amount of 4 × 10 ^-4 mol of 5- [3- (4.
-Sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt was added, and p-dodecylbenzenesulfonic acid sodium salt was further added. 300 mg and 15 g of styrene-maleic acid copolymer latex (average particle size of about 0.25 μm) were added, and Ag was added.
An amount of 4.0 g / m ² and a gelatin amount of 2.0 g / m ² were applied to the undercoated polyethylene terephthalate film base described in Example (1) of JP-A-59-19941. In addition, 800 mg / m ^{2 of} the compound T-3 shown in Table 1 was added as a tetrazolium compound. At that time as spreading agent so that gelatin amount 1.0 g / m ^2, bis -
(2-ethylhexyl) sulfosuccinate 10
mg / m ^2, a protective layer containing formalin 15 mg / m ² was simultaneously coated as a hardener. Obtained Samples 4-1 to 4-16
Sensitometry as shown below is performed, and sensitivity, γ, Dma
x was evaluated for fog.

<Exposure> Tungsten sensitometer 2854K 5 ″

(Composition A) Pure water (ion exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylribenzotriazole 200 mg 1-phenyl -5-Mercaptotriazole 30 mg Sodium hydroxide, an amount that makes the pH of the used solution 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid ( 90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 770 mg When the developer was used, the above composition A and composition B were dissolved in this order in 500 ml of water to make 1 liter.

<Fixer Formulation> (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90 % W / w aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% w / w aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ conversion content is 8.1% w / w Aqueous solution of 26.5 g When the fixing solution was used, the above composition A and composition B were dissolved in this order in 500 ml of water to make 1 liter. The pH of this fixer was about 4.3. The sensitivity, γ, and Dmax were taken as in Example 1, and the sensitivity of Sample 4-1 was set to 1. The results are shown in Table 5.

[0103]

[Table 5]

As is clear from Table 5, Samples 4-7 and 4-8 having the constitution of the present invention have the same γ and Dmax as those of Sample 4-2 in which the same amount of rhodium is added uniformly in total. so,
High sensitivity and low fog. Further, it can be seen that the samples 4-3 and 4-4 in which rhodium is added only to the core have high feeling and low fog. Regarding the samples using other heavy metals, as is clear from Table 5, the samples having the constitution of the present invention showed good performance with high feeling and low fog. Although not shown in the table, in the sample to which the tetrazolium compound of the present invention was not added, γ was about 7, and γ was insufficient as a photosensitive material for printing plate making.

Example 5 (Preparation of hydrazine-containing layer emulsion) Emulsions 2, 3, 7, 8, 15, and 16 used in Example 1 were the same as in Example 1, except that a sensitizing dye, a short-wave cyanine dye and mercapto were used. A compound, a triazine compound and the like were added, and further, 3 × 10 ⁻⁴ mol of a mercapto compound represented by the following structural formula (O) was added per mol of silver. To this, N-oleyl-N-methyltaurine sodium salt was added so as to be coated at 40 mg / m ² and 2 × 10 4 of A-4 was used as the hydrazine compound of the present invention.
^-3 mol added. Further, 1,2-bis (vinylsulfonylacetamido) ethane 50 mg / m ^{2 was} added as a polyethyl acrylate dispersion (500 mg / m ² ) hardener to prepare a hydrazine-containing layer coating solution.

[0106]

[Chemical 20]

(Preparation of Redox Compound-Containing Layer Emulsion) Glass
700 cc of silver nitrate aqueous solution in which 170 g of silver oxide is dissolved, and 1 silver
3 x 10 per mole ^-7Equivalent to mol (NH_Four)₃Rh
Cl₆Containing 36 g potassium bromide and sodium chloride
700cc of an aqueous solution of halogen salt in which 43g is dissolved is
Thorium (0.5%) and 1,3-dimethyl-2-imidazole
2% gelatin water containing Zolithion (0.002%)
Double jet method with stirring for 30 minutes at 45 ℃
The average grain size is 0.30 μm, and silver chloride is included.
70 mol% of silver chlorobromide grains were obtained. Then 1 mole silver
Per 1 x 10^-3Add a molar KI solution and
And water according to the standard method by flocculation.
Wash, add 40 g of gelatin per mol of silver, and adjust to pH 6.
0, pAg 7.6, and the amount of Ben
7 mg of sodium thiothiosulfonate and benzene sulfone
Phosphoric acid 2 mg, chloroauric acid 8 mg and sodium thiosulfate 5
mg was added, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization.
After that, 4-hydroxy-6-methyl-1, as a stabilizer,
350 mg 3,3a, 7-tetrazaindene and preservative
Was added as proxel. The obtained particles are average particle size
Silver chlorobromide with a size of 0.30 μm and a silver chloride content of 70 mol%
It was a cubic particle. (Coefficient of variation 9%)

Each of the emulsions thus obtained contained 5 × 10 ^-4 mol of 5- [3-mol as a sensitizing dye per mol of silver.
(4-Sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt was added, and the following structural formula (P) was added. 10 mg / m ^{2 of} a dye represented by
50 mg / m ²⁾ as a hardener 1,3-vinylsulfonyl-2-propanol (30mg / m ^2), was added as shown in Table 6 shown further after the redox compound B-19 of the present invention.

[0109]

[Chemical 21]

(Preparation of coating solution for intermediate layer) In a gelatin solution,
5 mg / m ^{2 of} sodium ethanethiosulfonate, 100 mg / m ^{2 of} dye represented by (Q), 100 of hydroquinone
50 mg / m ^{2 of} triol compound represented by (R)
A dispersion of m ² and polyethyl acrylate was added at 350 mg / m ² to prepare an intermediate layer coating solution.

[0111]

[Chemical formula 22]

Then, a layer of gelatin 0.2 g / m ² containing 40 mg / m ² of bis (vinylsulfonyl) methane was placed on the undercoated polyethylene terephthalate film, and a hydrazine-containing layer (Ag 3.4 g / m ² was used as the lowermost layer). ^2, gelatin 1.6 g / m ^2), via an intermediate layer (gelatin 1.2 g / m ^2), a layer containing a redox compound (Ag0.2g / m ^2,
Gelatin 0.2 g / m ² ), and further thereon 0.3 g / m ² of gelatin as a protective layer, 60 mg / m ^{2 of} amorphous SiO ₂ matting agent having an average particle size of about 3.5μ, 0.1 g of methanol silica / m ² , liquid paraffin 50 mg / m ² , coated with 5 mg / m ^{2 of} a fluorosurfactant represented by the structural formula (F) used in Example 1 as a coating aid and 20 mg / m ² of sodium dodecylbenzenesulfonate. Samples 5-1 to 5-12 shown in Table 6 below were prepared. Membrane surface pH of the obtained sample
Was 6.1. The back layer was applied in the same manner as in Example 1.

The evaluation was carried out in the same manner as in Example 1 for the sensitivity, γ, Dmax, and black spots, and the sensitivity was shown as 1 for Sample 5-1. Further, the stretched image quality was evaluated by the following method. (1) Manuscript preparation Monochrome scanner SCA manufactured by Fuji Photo Film Co., Ltd.
A transparent image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed stepwise were created using NART 30 and the special sensitive material SF-100. At this time, the number of screen lines was 150 lines / inch. (2) Photographing After setting the above originals on the plate-making camera C-440 manufactured by Dainippon Screen Co., Ltd. so that the stretching magnification is the same, Xe
The evaluation sample was exposed by illuminating the lamp. At this time, 95% of the step wedge of the original is 5
The exposure was performed so that it became%. (3) Good gradation reproducibility (difficulty in crushing halftone dots) of the shadow part of the sample in which halftone dots% on the small dot side (highlight part) where the exposure amount was adjusted as in the evaluation (2) were combined. Five-level evaluation (5 to 1) was performed in this order. The results are shown in Table 6.

[0114]

[Table 6]

Similar to Example 1, the sample having the constitution of the present invention has the same γ and Dmax as the comparative sample, and shows high sensitivity and good black spot performance. Further, it is understood that the image quality of stretched-out image is remarkably improved by the addition of the redox compound of the present invention.

[Procedure amendment]

[Submission date] July 27, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

The core / intermediate phase / outermost phase will be described below.
Gold contained in the halogen salt solution added during grain formation
Included in core / mesophase / outermost phase by changing the metal complex salt
Prepared silver halide grains with different metal species and amount
It was For example, for Emulsion-3, the halogen salt water used when preparing the core
2.7 × 10 per mol of silver contained in the solution ^-7
K equivalent to the mole₂Rh (H₂O) Cl_FiveAdd halo
Silver genide grains were prepared. The particles obtained are summarized in Table 2.
Showed. After grain formation, KI
It was converted, washed with water and chemically sensitized.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

[0082]

[Chemical 15]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0112

[Correction method] Change

[Correction content]

Then, on a polyethylene terephthalate film consisting of a moistureproof layer undercoating containing vinylidene chloride on both sides, a layer of gelatin 0.2 g / m ² containing 40 mg / m ² of bis (vinylsulfonyl) methane was used as the lowermost layer and a hydrazine containing layer. A layer containing a redox compound (Ag 0.2 g / m ² , gelatin 0.2 g) through a layer (Ag 3.4 g / m ² , gelatin 1.6 g / m ² ) and an intermediate layer (gelatin 1.2 g / m ² ). /
m ² ), and on top of this, 0.3 g of gelatin as a protective layer /
m ^2, average an amorphous SiO ₂ matting agent 60 mg / m ² of particle size of about 3.5 [mu], colloidal silica (manufactured by Nissan Chemical Industries, Ltd. Snowtex C) 0.1g / m ^2, liquid paraffin 50 mg /
m ² and 5 mg / m ^{2 of the} fluorosurfactant represented by the structural formula (F) used in Example 1 as a coating aid and 20 mg / m ² of sodium dodecylbenzenesulfonate were coated, and as shown in Table 6 below. Samples 5-1 to 5-12 were prepared. The film surface pH of the obtained sample was 6.1. The back layer was applied in the same manner as in Example 1.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer containing silver halide grains containing at least one of rhodium, rhenium, ruthenium, osmium and iridium on a support. The silver halide grains are composed of a core, an intermediate phase, and an outermost phase, and have at least one intermediate phase having a lower content of the metal than the core and the outermost phase, and hydrazine is contained in the emulsion layer or other hydrophilic colloid layer. A silver halide photographic light-sensitive material comprising a derivative or a tetrazolium compound. 2. A silver halide photographic light-sensitive material according to claim 1, which contains a hydrazine derivative, and further contains a redox compound which releases a development inhibitor by being further oxidized. material.