JPH0511389A - Silver halide photographic sensitive material and processing method thereof - Google Patents

Abstract

PURPOSE:To obtain the silver halide photosensitive material having a high sensitivity to an argon laser beam by chemically sensitizing photosensitive emulsion layers with a selenium compd. and incorporating specific compds. into the photosensitive emulsion layers. CONSTITUTION:The photosensitive emulsion layers of the silver halide photographic sensitive material having at least one layer of the photosensitive emulsion layers contg. silver halide particles are chemically sensitized with the selenium compd. In addition, the photosensitive emulsion layers contain at least one of the compds. expressed by formula I. In the formula I, R1, R2 respectively denote an alkyl group which may have a substituent; at least one of R1, R2 are an acetyl aminoalkyl group or N-alkyl carbomoyl aminoalkyl group. V1, V2 respectively denote a hydrogen atom, alkyl group, alkoxy group or trifluoromethyl group. The silver halide photographic sensitive material having the high sensitivity to the argon laser beam, decreased after-colors and excellent rapid processability is obtd. in this way.

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 having high sensitivity to argon laser exposure and excellent suitability for rapid processing, and a development processing method thereof. Is.

[0002]

2. Description of the Related Art One of the methods for exposing a photographic light-sensitive material is to scan an original image and expose it on a silver halide photographic light-sensitive material based on the image signal to obtain a negative or positive image corresponding to the image of the original image. There is known an image forming method by a so-called scanner method for forming an image. Although there are various recording apparatuses that actually use the image forming method using the scanner method, many so-called dot generator methods using a halftone dot generator are currently used. Conventionally, glow lamps, xenon lamps, mercury lamps, dangsten lamps, light emitting diodes and the like have been used as the recording light source of these scanner type recording apparatuses. However, each of these light sources has a practical drawback that the output is weak and the life is short. There is a scanner that uses a coherent laser light source such as a He—Ne laser, an argon laser, a He—Cd laser, and a semiconductor laser as a light source of a scanner system as a supplement to these drawbacks. Various properties are required for the light-sensitive materials used in these scanners, but since they are exposed by a short exposure time of 10 ^-3 to 10 ^-8 seconds, they are highly sensitive and have high sensitivity even under such conditions. Contrast is an essential condition. Further, in order to reduce the output in order to keep the life of the laser tube long, a highly sensitive photosensitive material is more advantageous. To obtain good halftone dots,
It is also necessary to shape the laser beam by using a slit or the like, and a high-sensitivity photosensitive material is required in order to deal with the laser output which is reduced by it. Above all, many scanners using an argon laser as a light source thereof are used because they can obtain a high output and a laser beam can be narrowed down. As a photosensitive material for an argon laser, it is common to use a technique called spectral sensitization by using a sensitizing dye having an absorption around 488 nm in order to give sensitivity to light of 488 nm which is the wavelength of the argon laser light. However, the residual color due to the sensitizing dye is often found in the processed light-sensitive material, which often lowers the commercial value of the finished product.

Further, in recent years, there has been a strong demand in the printing industry for work efficiency and speedup, and there is a wide range of needs for speeding up scanning and shortening the processing time of photosensitive materials. In order to meet the needs of these printing fields, it is desired that exposure machines (scanners, plotters) have faster scanning speeds and that the number of lines and beams be narrowed down to improve image quality. It is desired that the materials have high sensitivity, excellent processing stability, and rapid development processing. The rapid development process referred to here is the time after the leading edge of the film comes out of the drying section after passing through the developing tank, crossover section, washing tank and drying section after the leading edge of the film is inserted into the automatic developing machine. Say a process that is ~ 60 seconds.

The present inventor has found that selenium sensitization of silver halide is effective for these purposes.
This method alone has a problem that the residual color of the sensitizing dye at the time of rapid processing is observed after the processing.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light sensitive material having a high sensitivity to argon laser light. Another object of the present invention is to
An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity to an argon laser beam and having little residual color. Still another object of the present invention is to provide a silver halide photographic light-sensitive material which is highly sensitive to an argon laser light and gives a good image quality even if a rapid processing is carried out, and a development processing method thereof. Still another object of the present invention is to provide a silver halide photographic light-sensitive material which gives a high sensitivity to argon laser light and a good image quality even if the replenishment amounts of the developing solution and the fixing solution are reduced, and a development processing method thereof. It is in.

[0006]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer containing silver halide grains, wherein the light-sensitive emulsion layer is chemically treated with a selenium compound. This has been achieved by using a silver halide photographic light-sensitive material which is sensitized and which contains at least one compound represented by the following general formula (I) in the light-sensitive emulsion layer. General formula (I)

[0007]

[Chemical 2]

A specific configuration of the present invention will be described in detail. The silver halide photographic emulsion according to the present invention contains, as silver halide, silver chloride, silver chlorobromide, silver bromide, silver iodobromide or silver chloroiodobromide. At this time, it is preferable to contain silver chloride in an amount of 30 mol% or more, more preferably 60 mol% or more. The shape of silver halide grains is cubic, tetradecahedral,
It may be an octahedron, an amorphous type, or a plate shape, but a cubic or plate shape is preferable. The average grain size of silver halide grains is 0.0
1 μm to 1 μm is preferable, but 0.4 μm is more preferable.
m or less, {(standard variation of particle size) / (average particle size)}
The coefficient of variation represented by × 100 is preferably 15% or less, more preferably 10% or less, and the particle size distribution is narrow. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases. The photographic emulsion used in the present invention is a Chimie et Physique Ph by P. Glafkides.
otographique (Paul Montel, 1967), GF
Photographic Emulsion Chemistry (The Focal by Duffin
Press, 1966), by VL Zelikman et al Mak
ing and Coating Photographic Emulsion (The Focal Pr
ess, 1964) and the like. That is, any of the acidic method, the neutral method, the ammonia method and the like may be used, and as the formation of reacting the soluble silver salt and the soluble halogen salt, any one of the one-side mixing method, the 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 where 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, British Patent No. 1,535,016 and Japanese Patent Publication No. 48-
36890 and 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent 4,24.
No. 2,445, JP-A-55-158124, a method of changing the concentration of an aqueous solution is used.
It is preferable to grow quickly in a range not exceeding the critical saturation. The grain formation of the silver halide emulsion of the present invention is
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
It is a compound represented by the following general formula (II) described in JP-A Nos. 53-82408 and 55-77737. General formula (II)

[0009]

[Chemical 3]

The general formula (II) will be described. Where R
₁ , R ₂ , R ₃ and R ₄ represent a substituted or unsubstituted alkyl group, an alkenyl group (such as an allyl group) or a substituted or unsubstituted aryl, which may be the same or different from each other; The total number of carbon atoms of _{1 to} R ₄ is 30
The following are preferred. Further, it is also possible to combine with R ₁ and R ₂ , R ₂ and R ₃ , or R ₃ and R ₄ to form a 5- or 6-membered heterocyclic imidazolidinethione, piperidine, morpholine and the like. Both straight-chain and branched alkyl groups are used. Examples of the substituent of the alkyl group include a hydroxy group (-OH), a carboxy group, a sulfonic acid group, an amino group, an alkoxy group (o-alkyl) having an alkyl residue having 1 to 5 carbon atoms, a phenyl group or It is a 5- or 6-membered heterocycle (such as furan). The substituent of the aryl group is a hydroxy group, a carboxy group or a sulfonic acid group. Here, particularly preferably, R ₁
To R ₄ are three or more alkyl groups, each alkyl group has 1 to 5 carbon atoms, the aryl group is a phenyl group, and further R
The total number of carbon atoms of _{1 to} R ₄ is 20 or less. Examples of the compound that can be used in the present invention include the following.

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

The organic thioether silver halide solvent preferably used in the present invention is, for example, JP-B-47-11386.
No. (U.S. Patent No. 3,574,628) comprising at least one compound group wherein oxygen atom and a sulfur atom are separated by an ethylene (e.g. -O-CH ₂ CH ₂ -S-) in the like, especially Alkyl groups at both ends described in Kai 54-155828 (U.S. Pat. No. 4,276,374), each of which is at least 2 selected from hydroxy, amino, carboxy, amido or sulfone.
It is a chain thioether compound having one substituent). Specifically, the following examples can be given.

[0016]

[Chemical 8]

The amount of the silver halide solvent added varies depending on the kind of the compound used, the intended grain size, the halogen composition, etc., but is from 10 ^-5 to 1 mol per mol of the silver halide.
10 ^-2 mol is preferred. If the grain size becomes larger than intended by using a silver halide solvent, the temperature during grain formation,
A desired particle size can be obtained by changing the addition time of the silver salt solution or the halogen salt solution.

It is preferable to use an iridium compound in the silver halide emulsion of the present invention. As the iridium compound used in the present invention, a water-soluble iridium compound can be used. For example, iridium (III) halide
Compounds, iridium (IV) halide compounds, and iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (III) or (IV) complex salts, hexaammineiridium (III) or ( IV) complex salt, trioxalatoiridium (III) or (IV) complex salt. In the present invention, any of these compounds may be used in any combination of a trivalent compound and a trivalent compound. These iridium compounds are used by dissolving them in water or a suitable solvent, and a method that is generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) , Or an alkali halide (eg KCl, NaCl, KBr, NaB
r etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide grain. The total addition amount of the iridium compound according to the present invention is 1 × 10 ⁻⁸ to 1 × 10 1 per mol of finally formed silver halide.
^-6 mol is suitable, preferably 5 x 10 ^-8 to 1 x 10
^-6 mol. The addition of these compounds can be appropriately carried out at the time of producing the silver halide emulsion and at each stage before coating the emulsion, but in particular, it can be added at the time of grain formation and incorporated into the silver halide grains. preferable. Specific compounds include iridium chloride (II
I), primary iridium (III) bromide, secondary iridium chloride (IV), sodium hexachloroiridium (III),
Halogen amines such as hexachloroiridium (III) salt, hexaamineiridium (IV) salt, trioxalatoiridium (III) salt and trioxalatoiridium (IV) salt, and oxalato complex salts are preferable.

An iron compound is preferably used in the silver halide emulsion of the present invention. The iron compound used in the present invention is a divalent or trivalent iron ion-containing compound, and is preferably an iron salt or an iron complex salt having water solubility in the concentration range used in the present invention. Specifically, ferrous arsenate ferrous bromide ferrous carbonate ferrous chloride ferrous citrate ferrous fluoride ferrous formate ferrous gluconate ferrous ferrous hydroxide iodide ferrous Ferrous lactate ferrous oxalate ferrous phosphate ferrous succinate ferrous sulfate ferrous thiocyanate ferrous nitrate ferrous nitrate ammonium basic ferric acetate ferric albumin ferric acid Ferric acetate ammonium ferric bromide ferric chloride chlorate ferric citrate ferric fluoride ferric formate ferric glycerophosphate ferric hydroxide ferric hydroxide acidic phosphate ferric Ferric nitrate ferric phosphate ferric pyrophosphate ferric pyrophosphate ferric sodium sodium ferric thiocyanate ferric sulfate ferric ammonium sulfate ferric ammonium sulfate ferric acid guanidine ferric ammonium hexane cyanoferric acid (II) Potassium benthacyanoammine ferrous potassium ethylenedinitrilotetraacetic acid secondary Sodium hexacyanoferrate iron (III) potassium chloride tris (dipyridyl) ferric preventor cyano nitrosyl ferric potassium chloride Hekisarea ferric particularly hexacyanoferrate (II), hexacyanoferrate (III)
Acid salts, ferrous thiocyanate and ferric thiocyanate show remarkable effects.

Rhenium, ruthenium and osmium compounds can be used in the emulsion of the present invention. The rhenium, ruthenium and osmium compounds used in the present invention are European open patents (EP) 0336689A, 0336427A1, 0336425A1 and 0.
The hexadentate coordination complex described in No. 336426A1 is preferable, and one containing at least 4 or more cyanide ligands is particularly preferable. In a preferred embodiment, these compounds can be represented by the formula: [M (CN) _6-y L _y ] ⁿ where M is rhenium, ruthenium, osmium, L is a bridging ligand, y is an integer 0, 1, or 2, and n is -2. , -3 or -4. As a specific example, [Re (CN) ₅ ] ^-4 [Ru (CN) ₅ ] ^-4 [Os (CN) ₅ ] ^-4 [ReF (CN) ₅ ] ^-4 [RuF (CN) ₅ ] ^-4 [ OsF (CN) ₅ ] ^-4 [ReCl (CN) ₅ ] ^-4 [RuCl (CN) ₅ ] ^-4 [OsCl (CN) ₅ ] ^-4 [ReBr (CN) ₅ ] ^-4 [RuBr (CN) ₅ ] ^-4 [OsBr (CN) _5] ^-4 [ReI (CN) _5] ^-4 [RuI (CN) _5] ^-4 [OSI (CN) _5] ^-4 [ReF ₂ (CN) _4] ^-4 [ RuF ₂ (CN) ₅ ] ^-4 [OsF ₂ (CN) ₅ ] ^-4 [ReCl ₂ (CN) ₄ ] ^-4 [RuCl ₂ (CN) ₄ ] ^-4 [OsCl ₂ (CN) ₄ ] ^-4 [ RuBr ₂ (CN) ₄ ] ^-4 [OsBr ₂ (CN) ₄ ] ^-4 [ReBr ₂ (CN) ₄ ] ^-4 [RuI ₂ (CN) ₄ ] ^-4 [OsI ₂ (CN) ₅ ] ^-4 [ Ru (CN) ₅ (OCN)] ^-4 [Os ( CN) ₅ (OCN)] ^-4 [Ru (CN) ₅ (SCN)] ^-4 [Os (CN) ₅ (SCN)] ^-4 [Ru (CN) ₅ (N ₃ )] ^-4 [Os (CN ) ₅ (N ₃ )] ^-4 [Ru (CN) ₅ (H ₂ O)] ^-3 [Os (CN) ₅ (H ₂ O)] ^-3 .

The above iron, rhenium, ruthenium and osmium compounds are preferably added during the formation of silver halide grains. The addition position may be evenly distributed in the particles, or may be localized in the early, middle, and late stages of particle formation.
It is preferred to add after 0%, more preferably 80% is formed. The addition amount is 10 ^-3 mol or less per 1 mol of silver, and preferably 10 ^-6 to 10 ^-4 mol. In the present invention, other metals contained in Group VIII, that is, cobalt, nickel, rhodium, palladium, platinum and the like may be used in combination. In particular, the combined use with a rhodium salt such as rhodium chloride or ammonium hexachlorodium (III) is advantageous because a high contrast emulsion can be obtained.

The compound represented by formula (I) used in the light-sensitive material of the present invention will be described. General formula (I)

[0023]

[Chemical 9]

Here, R ₁ and R ₂ are each an alkyl group (having 4 or less carbon atoms, for example, methyl group, ethyl group, 3-
Propyl group, 3-butyl group, 4-butyl group, etc.), substituted alkyl group [having 4 or less carbon atoms in the alkyl moiety, for example, sulfoalkyl group (eg, sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4- Sulfobutyl group), carboxyalkyl group (eg carboxymethyl group, carboxyethyl group, 3-carboxypropyl group etc.), hydroxyalkyl group (eg hydroxymethyl group, hydroxyethyl group etc.), aralkyl group (eg benzyl group, phenethyl group) , Sulfophenethyl group etc.), aryloxyalkyl group (eg phenoxyethyl group, phenoxypropyl group, sulfophenoxypropyl group etc.), acetylaminoalkyl group (eg 2-acetylaminoethyl group, 3-acetylaminopropyl group etc.), Alkyls Fonylaminoalkyl group (for example, 2-methylsulfonylaminoethyl group, 3-methylsulfonylaminopropyl group, etc.), N-alkylcarbamoylaminoalkyl group [for example, 2- (N-methylcarbamoyl) aminoethyl group, 2- (N -Ethylcarbamoyl) aminoethyl group, 3- (N-methylcarbamoyl)
Aminopropyl group) and at least one of R ₁ and R ₂ is an acetylaminoalkyl group or an N-alkylcarbamoylaminoalkyl group. V ₁ , V
₂ represents a hydrogen atom, an alkyl group (having 3 or less carbon atoms, such as a methyl group, an ethyl group, etc.), an alkoxy group (having 3 or less carbon atoms, such as a methoxy group, an ethoxy group, etc.), and a trifluoromethyl group. Specific examples of the compound represented by formula (I) of the present invention are shown below.

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical 12]

[0028]

[Chemical 13]

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
No. 2, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-22930
It is preferable to use the compounds described in No. 0 and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And so on. The preferred types of labile selenium compounds have been described above, but are not limiting. To those skilled in the art, when it comes to unstable selenium compounds as sensitizers for photographic emulsions, the structure of the compounds is not so important as long as selenium is unstable,
It has generally been solved that the organic part of the selenium sensitizer molecule carries selenium and plays no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention include JP-B-46-4553 and JP-B-52-344.
The compounds described in JP-B No. 92 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (III) and (IV) are preferable. General formula (III)

[0030]

[Chemical 14]

In the formula, Z ₁ and Z _{2, which} may be the same or different, each represents an alkyl group (for example, a methyl group,
Ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg vinyl group, propenyl group), aralkyl group (eg benzyl group, phenethyl group), aryl group (eg phenyl group) , Pentafluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -NR ₁ (R ₂ ),-
Represent OR ₃ or -SR _4. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R
₁ and R ₂ are a hydrogen atom or an acyl group (for example, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoromethylbenzoyl group ) May be sufficient. In formula (III), Z ₁ is preferably an alkyl group, an aryl group or —NR
₁ (R ₂ ), Z ₂ represents —NR ₅ (R ₆ ). R ₁ ,
R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. In the general formula (III), more preferably N, N
-Dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents an alkyl-N-aryl-arylselenoamide. General formula (IV)

[0032]

[Chemical 15]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₇ , -NR ₈ (R ₉ ), -SR. ₁₀ , -Se
R ₁₁ , X and a hydrogen atom are represented. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. , X represents a halogen atom. In the general formula (IV), Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ ,
The aliphatic group represented by R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (eg, methyl group, ethyl group, n-group).
Propyl group, isopropyl group, t-butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentyl group Pentenyl group, propargyl group, 3-pentynyl group, benzyl group, phenethyl group). In the general formula (IV), Z ₃ , Z ₄ , Z ₅ ,
The aromatic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (for example, a phenyl group,
Pentafluorophenyl group, 4-chlorophenyl group, 3
-Sulfophenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (IV), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (eg, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group). In the general formula (IV), the cations represented by R ₇ , R ₁₀ and R ₁₁ represent an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Represents In general formula (IV), preferably Z ₃ , Z ₄ or Z ₅
Represents an aliphatic group, an aromatic group or —OR ₇ , and R ₇ represents an aliphatic group or an aromatic group. In formula (IV), more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of the compounds represented by formulas (III) and (IV) are shown below, but the invention is not limited thereto.

[0034]

[Chemical 16]

[0035]

[Chemical 17]

[0036]

[Chemical 18]

[0037]

[Chemical 19]

[0038]

[Chemical 20]

[0039]

[Chemical 21]

[0040]

[Chemical formula 22]

[0041]

[Chemical formula 23]

Regarding the selenium sensitization method, US Pat.
No. 74944, No. 1602592, No. 16234
No. 99, No. 3297446, No. 3297447
No. 3320069, No. 3408196, No. 3408197, No. 3442653, No. 34.
No. 20670, No. 3591385, French Patent No. 2693038, No. 2093209, Japanese Patent Publication No. 52
-34491, 52-34492, and 53-29.
5, 57-22090, and JP-A-59-18053.
No. 6, No. 59-185330, No. 59-181337.
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, JP-A-3-42221,
Japanese Patent Application Nos. 1-287380, 1-250950, 1-254441, 2-334090 and 2-11
No. 0558, No. 2-130976, No. 2-13918
No. 3, No. 2-229300, and British Patent No. 2558.
46, No. 861984 and H.H. E. Spencer et al., Journal of Photographic Science, Vol. 31, 1
58-169 (1983) and the like.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or they are disclosed in Japanese Patent Application Nos. 2-264447 and 2-26.
It is added at the time of chemical sensitization in the form described in No. 4448.
It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, etc. It is 1 × 10 ⁻⁸ mol or more per mol. It is more preferably 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when the selenium sensitizer is used is preferably 4
It is 5 ° C or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9.

Selenium sensitization is more effective when carried out in the presence of a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include US Pat.
271,157, 3,531,289, 3,574,628, and JP-A-54-1019, 5
(A) Organic thioethers described in JP-A-4-158917, JP-A-53-82408 and JP-A-55-7773.
No. 7, 55-2982 and the like (b) thiourea derivatives, and (c) the thiocarbonyl group described in JP-A No. 53-144319 (c) sandwiched between an oxygen or sulfur atom and a nitrogen atom. Silver halide solvent having
(D) imidazoles described in No. 100717,
(E) Sulfite, (f) thiocyanate and the like. Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol of silver halide. The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. For sulfur sensitization, known sulfur sensitizers can be used. Examples thereof include thiosulfates, thioureas, allyl isothiocyanates, cystines, p-toluene thiosulfonates, and rhodanines. Other US Pat. Nos. 1,574,944 and 2,41
No. 0,689, No. 2,278,947, No. 2,7
No. 28,668, No. 3,501,313, No. 3,
656,955 specifications, German Patent 1,422,8
No. 69, Japanese Patent Publication No. 56-24937, and Japanese Patent Laid-Open No. 55-45.
The sulfur sensitizers described in JP-A No. 016, etc. can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but it is 1 × 10 ^-7 mol or more per 5 mol of silver halide and 5 × 10 ^-4. It is preferably not more than mol. As the gold sensitizer for the above gold sensitization, the oxidation number of gold is +1.
The valency may be +3 or +3, and a gold compound usually used as a gold sensitizer may be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide. At the time of chemical ripening, it is not necessary to particularly limit the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. Alternatively, for example, the above compounds can be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical ripening or at different addition points. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, acetone or the like and added.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzothiazoles, nitrobenzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes; eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) Tetrazaindenes), pentaazaindenes, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. You can Particularly, a polyhydroxybenzene compound is preferable because it improves pressure resistance without impairing sensitivity. The polyhydroxybenzene compound is preferably a compound having any of the following structures. General formula (V)

[0046]

[Chemical formula 24]

Next, the general formula (V) will be described. X and Y are -H, -OH, a halogen atom, -OM (M
Is an alkali metal ion), -alkyl group, phenyl group,
Amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated alkyl group, sulfonated amino group,
A sulfonated carbonyl group, a carboxyphenyl group, a carboxyalkyl group, a carboxyamino group, a hydroxyphenyl group, a hydroxyalkyl group, an alkyl ether group, an alkylphenyl group, an alkylthioether group, or a phenylthioether group. Below, the general formula (V)
Specific examples of the compound are shown below.

[0048]

[Chemical 25]

[0049]

[Chemical formula 26]

[0050]

[Chemical 27]

The polyhydroxybenzene compound may be added to the emulsion layer in the light-sensitive material or to a layer other than the emulsion layer. The addition amount is effectively in the range of 10 ^-5 to 1 mol, and particularly effective in the range of 10 ^-3 to 10 ^-1 mol, per 1 mol. The light-sensitive material produced by using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes,
Cyanine dyes and azo dyes are included. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development,
For example, polyalkylene oxide or its ether,
Derivatives such as esters and amines, thioether compounds,
Developers such as thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones and aminophenols may be included. Among them, 3-pyrazolidones (1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like) are preferable,
Usually used at 5 g / m ² or less, 0.01 to 0.2 g / m ²
Is more preferable. The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N-methylenebis-
[Β- (vinylsulfonyl) propionamide] and the like), active halides (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalogen acids (mucochloric acid and the like), N-carbamoylpyridinium salts (1- Morpholi) carbonyl-3-pyridinio) methanesulfonate, etc.), haloamidinium salts (1- (1
-Chloro-1-pyridinomethylene) pyrrolidinium, 2
-Naphthalene sulfonate, etc.) alone or in combination. Among them, JP-A-53-41
220, 53-57257, 59-16254.
Active vinyl compounds described in JP-A Nos. 6 and 80-8046 and active halides described in US Pat. No. 3,325,287 are preferable. For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration, contrast enhancement). For various purposes such as sensitization), various surfactants may be included. For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic surfactants such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphorus Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups such as acid esters; amino acid salts, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid Amphoteric surfactants such as esters, alkylbetaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Further, in order to prevent electrification, JP-A-60-80849 is used.
It is preferable to use the fluorine-containing surfactants described in No.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethylmethacrylate in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of preventing adhesion. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, alkyl (meth)
A polymer having a monomer component of acrylate, alkoxyacrylic (meth) acrylate, glycidyl (meth) acrylate, or a combination thereof, or a combination thereof with acrylic acid, methacrylic acid, or the like can be used. Gelatin is advantageously used as the condensing agent or protective colloid for the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. The silver halide emulsion layer used in the present invention may contain a polymer latex such as an alkyl acrylate. As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper and the like can be used.

The developing agent used in the developing solution used in the present invention is not particularly limited, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl are preferable. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable. 1-phenyl-used in the present invention
As a developing agent for 3-pyrazolidone or its derivative, 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- There is pyrazolidone. As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N
-(Β-hydroxyethyl) -p-aminophenol,
There are N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like, and among them, N-methyl-p-aminophenol is preferable. The developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. Also, dihydroxybenzenes and 1-phenyl-3-
When the combination with pyrazolidones or p-amino-phenols is used, the former is 0.05 mol / liter-
It is preferable to use 0.5 mol / liter and the latter in an amount of 0.06 mol / liter or less. Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. 0.3 mol / sulfite
It is preferably at least liter, particularly at least 0.4 mol / liter. The upper limit is up to 2.5 mol / liter, especially 1.
It is preferably up to 2. Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate,
Includes pH adjusters and buffers such as potassium triphosphate, sodium silicate, potassium silicate. As additives used in addition to the above components, boric acid, compounds such as borax,
Development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol,
Organic solvents such as triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-
Mercapto compounds such as 5-sulfonic acid sodium salt,
Indazole-based compounds such as 5-nitroindazole, 5
-An antifoggant such as a benztriazole-based compound such as methylbenztriazole may be contained, and if necessary, a toning agent, a surfactant, an antifoaming agent, a water softener, a film hardener and the like may be contained. Particularly, JP-A-56-10624
The amino compounds described in No. 4 and the imidazole compounds described in JP-B-48-35493 are preferable from the viewpoint of promoting development or increasing sensitivity. In the developer used in the present invention, the compounds described in JP-A-56-24347 are used as the silver stain preventing agent, and the development unevenness preventing agent (JP-A-62-21).
2, 651), and the compounds described in JP-A-61-267759 can be used as dissolution aids.

The fixing solution is an aqueous solution containing a hardening agent (for example, a water-soluble aluminum compound), acetic acid and a dibasic acid (for example, tartaric acid, citric acid or salts thereof), if necessary, in addition to the fixing agent, and preferably. , PH. It has 8 or more, more preferably 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed, and is generally about 0.1
It is about 5 mol / liter. The water-soluble aluminum salt mainly used as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective that these compounds are contained in an amount of 0.005 mol or more per liter of the fixing solution, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like can be given. Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. If desired, the fixer may contain preservatives (eg, sulfite, bisulfite),
A pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), an image preservation improving agent (eg, potassium iodide), and a chelating agent can be included. Since the pH of the developer is high, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably 18 to 25 g / liter. The light-sensitive material of the present invention exhibits excellent performance in rapid development processing by an automatic processor having a pretreatment time of 15 to 60 seconds. In the rapid development process of the present invention, the temperature and time for development and fixing are each 25 seconds or less at about 25 ° C to 50 ° C, preferably 30 ° C to 40 ° C for 4 seconds to 15 seconds.

In the present invention, the light-sensitive material is developed and fixed and then washed with water or stabilized. Here, in the water washing step, water saving treatment can be performed by using a countercurrent water washing method of two or three stages. Further, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank. Further, a part or the whole of the overflow solution from the washing bath or the stabilizing bath can be used as the fixing solution as described in JP-A-60-235133. This is more preferable because the amount of waste liquid is reduced. Further, in the washing water, antifungal agents (eg, compounds described in Horiguchi, Chemistry of antibacterial and antifungal, JP-A No. 62-115154), washing accelerators (sulfites, etc.), chelating agents, etc. It may be contained. The temperature and time of the water washing or stabilizing bath according to the above method are 0 ° C to 50 ° C for 5 seconds to 30 seconds, preferably 15 ° C to 40 ° C for 4 seconds to 20 seconds. In the present invention, the photosensitive material which has been developed, fixed and washed with water is dried through a squeeze roller. Drying is 40 ℃ ～ 80 ℃ for 4 seconds ～
It takes 30 seconds. With the total processing time in the present invention, after inserting the tip of the film into the insertion port of the automatic developing machine, a developing tank, a transition portion, a fixing tank, a transition portion, a washing tank, a transition portion,
It is the total time from passing through the drying section to exiting from the drying outlet from the leading edge of the film. The reducing liquid used in the present invention is not particularly limited, and for example, those described in "The Theory of the Photos Processes" by Mies can be effectively used. That is, permanganate, persulfate, ferric salt, cupric salt, cerium salt, red blood salt, dichromate, etc. may be used alone or in combination, and if necessary, sulfuric acid or the like. Solution containing inorganic acids and alcohols, or reducing agents such as red blood salt, ferric ethylenediaminetetraacetic acid salt and silver halides such as thiosulfate, rhodan salt, thiourea or its derivatives A reducing solution containing a solvent and, if necessary, an inorganic acid such as sulfuric acid is used. The reducing solution used in the present invention may further contain a compound having a mercapto group as described in JP-A-52-68419, if necessary. The composition of the reducing liquid used for the reducing treatment of the present invention and the treatment conditions (temperature, time, etc.) are not particularly limited and can be appropriately determined by those skilled in the art. Regarding the reducing liquid and the reducing method, the descriptions in the following patents can be referred to. JP-A-51-140733 and JP-A-52-684
No. 19, No. 53-14901, No. 54-119236.
No. 54-119237, No. 55-2245, No. 55-2244, No. 55-17123, No. 55-7.
No. 9444, No. 55-81344 Hereinafter, the present invention will be described more specifically with reference to Examples.

[0057]

【Example】

Example 1 Preparation of Emulsion A 1 liquid water 1.0 liter gelatin 20 g sodium chloride 20 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenethiosulfonate 6 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml chloride Sodium 30.5 g Potassium bromide 14.0 g Ammonium hexabromorhodium (III) 1.5 ml (0.001% aqueous solution) While stirring liquids 2 and 3 in liquid 1 kept at 38 ° C and pH 4.5. Simultaneously added over 10 minutes, 0.16 μm
Core particles were formed. Then, the following 4 liquid and 5 liquid were added over 10 minutes. Further, 0.15 g of potassium iodide was added to complete grain formation. 4-liquid water 400 ml Silver nitrate 100 g 5-liquid water 400 ml Sodium chloride 30.5 g Potassium bromide 14.0 g Potassium hexachloroiridium (III) ate 15 ml (0.001% aqueous solution) Then washed with water according to the conventional method Then, 30 g of gelatin was added.

This was divided into two equal parts, the pH was adjusted to 5.5 and the pAg was adjusted to 7.5, 3.7 mg of sodium thiosulfate and 6.2 mg of chloroauric acid were added, and optimum sensitivity was obtained at 65 ° C. Chemically sensitized. One emulsion had a pH of 5.3 and a pAg of 7.
Adjust to 5, 2.6 mg of sodium thiosulfate and 1.0 mg of N, N-dimethylselenourea, 4 mg of sodium benzenethiosulfonate and 1 mg of sodium benzenesulfinate to obtain optimum sensitivity at 55 ° C. Chemically sensitized. 2-methyl-4hydroxy-1,3,3a as a stabilizer,
200 mg of 7-tetraazaindene was added to finally obtain a silver iodochlorobromide cubic emulsion containing 80 mol% of silver chloride and having an average particle diameter of 0.20 μm. (Coefficient of variation 9%)

Preparation of Emulsion B The above emulsion A and washing gelatin are added in the same manner. This was divided into two equal parts, the pH was adjusted to 5.5, the pAg was adjusted to 7.5, and 3.7 mg of sodium thiosulfate and 6.2 mg of chloroauric acid were added, and chemical sensitization was performed at 65 ° C. to obtain the optimum sensitivity. One emulsion had its pH adjusted to 5.3 pAg to 7.5 and sodium thiosulfate 2.
6 mg and 3.0 mg of triphenylphosphine selenide were added, 4 mg of benzenethiosulfonic acid soda was added, and 1 mg of sodium benzenesulfinate was added, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity. 2-Methyl-4-hydroxy-1,3,3a, 7-tetraazaindene 200 as a stabilizer
Finally, a silver iodochlorobromide cubic emulsion containing 80 mol% of silver chloride and having an average particle diameter of 0.20 μm was obtained. (Coefficient of variation: 9%) Preparation of coated sample As shown in Table 1, 5 × 10 5 of ortho sensitizing dye was added to the above emulsion.
Ortho sensitization was performed by adding ^-4 mol / mol Ag. Further, as antifoggants, hydroquinone, 1-phenyl-5-
2.5 g and 50 mg of mercaptotetrazole per AgI mol, respectively, 25% of gelatin binder ratio of polyethyl acrylate latex as a plasticizer, and 2-bis (vinylsulfonylacetamide) ethane as a hardening agent were added to form Ag3 on the polyester support. 0.0 g / m ² ,
The gelatin was applied so as to be 1.0 g / m ² . A protective layer was simultaneously coated on this. At this time, a matting agent (polymethylmethacrylate having an average particle size of 3.4 μm) was added as a non-photosensitive upper layer in an amount of 0.10 g / m ² and a coated gelatin amount of 0.5 g / m ^2. P as a coating aid
-Sodium dodecylbenzene sulfonate and structural formula (VI-
The Fluorosurfactant of 1) was added and the emulsion layer was coated at the same time.

[0060]

[Chemical 28]

The support of the sample used in this example has a back layer and a back protective layer having the following compositions. Back layer Gelatin 2.0 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Dye (VI-2) 70 mg / m ² Dye (VI-3) 70 mg / m ² Dye (VI-4) 90 mg / m ² 1, 3-divinylsulfonyl-2-propanol 60 mg / m ²

[0062]

[Chemical 29]

[0063] Back protective layer Gelatin 0.5 g / m ² Polymethyl methacrylate (particle size 4.7 [mu] m) 30 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² containing fluorine surfactant (VI-1) 2mg / m 2 Silicone oil 100mg / m ²

Evaluation of sample The obtained sample was exposed to a xenon flash light having an emission time of 10 ^-5 sec by interposing an interference filter having a peak at 488 nm, and an automatic processor FG manufactured by Fuji Photo Film Co., Ltd. was used.
Sensitometry was performed using -710NH at the temperature and time indicated below. However, the developing solution and the fixing solution are LD835 and LF308 manufactured by Fuji Photo Film Co., Ltd., respectively.
Was used. Development 38 ° C 14 seconds fixing 37 ° C 9.7 seconds washing 26 ° C 9 seconds squeeze 2.4 seconds drying 55 ° C 8.3 seconds total 43.4 seconds Density of 3.0 gives the reciprocal of the exposure amount as the sensitivity Are shown in Table 1. In addition, the concentration of 0.1 and 3.0 in the characteristic curve
The inclination of the straight line connecting the points is also shown in Table 1 as gradation. Evaluation of Residual Color The washing temperature was changed to 5 ° C. under the above processing conditions, and the degree of coloring by the dye remaining in the processed photosensitive material was evaluated. In the table, 5, 4, 3, 2, and 1 are shown, and 5 and 4 are acceptable.
1 is an impossible level.

[0065]

[Table 1]

[0066]

[Chemical 30]

[0067]

[Table 2]

As can be seen from Tables 1 and 2, the present invention has high feeling, low fog and rapid processability.

Example 2 The following developing solution and fixing solution were placed in an automatic processor FG710NH, and the amount of coated silver was 3.6 g / m ² and the halogen composition was 70 mol% of chlorine.
The silver chlorobromide film was treated with 150 m ² while replenishing the following developing solution and fixing solution at 180 cc / m ² under the condition that the blackening rate was 50%. Samples similar to Nos. 1 to 8 of Example 1 were passed through the liquid and evaluated. The results are shown in Table 3.

[0070] (Developer) g / liter (use liquid)   Potassium hydroxide 24   Potassium sulfite 70   Diethylenetriamine pentaacetic acid 2.4   Boric acid 10   Hydroquinone 35   Diethylene glycol 11.2   4-hydroxymethyl-4-methyl-1-     Phenyl-3-pyrazolidone 2.5   5-methylbenzotriazole 0.06   pH 10.05 (Fixer)   Fixer A   Ammonium thiosulfate 150 g / liter   Compound (VII-1) 0.25 mol / liter   Sodium bisulfite 30 g / liter   Ethylenediaminetetraacetic acid disodium dihydrate 0.025 g / liter Adjust pH to 6.0 with sodium hydroxide

[0071]

[Chemical 31]

[0072]

[Table 3]

As can be seen from Table 3, even if the replenishment amounts of the developing solution and the fixing solution are reduced to 200 cc / m ² or less, the present invention has high hardness and low residual color, and is suitable for rapid processing.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer containing silver halide grains on a support, said light-sensitive emulsion layer being chemically sensitized with a selenium compound, and A silver halide photographic light-sensitive material comprising a light-sensitive emulsion layer containing at least one compound represented by the following general formula (I). General formula (I) In the formula, R ₁ and R ₂ each represent an alkyl group which may have a substituent, and at least one of R ₁ and R ₂ is an acetylaminoalkyl group or an N-alkylcarbamoylaminoalkyl group. V ₁ and V ₂ each represent a hydrogen atom, an alkyl group, an alkoxy group or a trifluoromethyl group. 2. The method for developing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is carried out by an automatic processor having a total processing time of 15 seconds to 60 seconds. 3. The development processing method of a silver halide photographic light-sensitive material according to claim 1, wherein the processing is carried out by using an automatic processor having a line speed of 1000 mm / min or more. 4. The replenishing amounts of the developing solution and the fixing solution are each 200.
4. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is carried out by using an automatic processor having a cc / m ² or less.