JPH06308652A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make possible rapid processing and to enhance sensitivity and storage stability with the lapse of time, especially, in the case of storage changing from cold temperature like in a refrigerator or the like to near room temperature by incorporating a specified gold compound in silver halide grains. CONSTITUTION:The silver halide grains in a photographic emulsion comprise >=95mol% silver chloride and they are sensitized by a kind of sensitization process selected from selenium and tellurium sensitizations and reduction sensitization, and they contain in the insides of them a kind of gold compound represented by one of formulae I-III in which Y is H or a cation; L is a 5- or 6-membered heterocyclic ligand; X is an anion; m is 0, 1, or 2; n is 1 or 2; p is 0, 1, 2, or 3; q is 1, 2, or 3; r is 1, 2, 3, or 4; each of R, V, If, and Y is H or the like; X is an ion for cancelling an intramolecular charge; each of l, m, and n in formulae II and III is an integer of 1-3, 2 or 3, and a number of ions for cancelling an intramolecular charge, respectively,.

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 which is capable of rapid processing, has high sensitivity and has a small sensitivity variation with time. More specifically, it uses an emulsion containing a high concentration of silver chloride and has high sensitivity and stability over time, especially storage stability when conditions change between low temperature conditions such as a refrigerator and temperature conditions near room temperature. And a silver halide photographic light-sensitive material excellent in

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials, especially silver halide color photographic light-sensitive materials are used very much today because of their high sensitivity and excellent gradation.

However, the development processing of the silver halide color photographic light-sensitive material is a so-called wet processing, and it takes time to prepare the processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, and a dark room is required. There are drawbacks such as a long time from the start of the operation until the first print is obtained. In order to compensate for these drawbacks and make full use of the advantages of the silver halide color photographic light-sensitive material described above, so far, engineers who have been skilled in everything from the development of color negatives to the production of color prints have focused exclusively on a small number of large development laboratories. The method of doing has been adopted.

This system is a so-called negative-positive system in which a silver halide photographic light-sensitive material for printing is exposed and developed through an image recorded on a color negative film, which is due to excess or deficiency of exposure and difference in illumination when photographing with a color negative. Since it is possible to correct the color misregistration at the time of printing, it has become possible to stably provide a high-quality printed image.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic processors, improvements in processing solutions, improvements in silver halide color photographic light-sensitive materials and packaging forms thereof have been accumulated. Therefore, a so-called minilab, which is capable of consistently performing color negative development to color print production in a small space such as at a photo shop, is rapidly becoming popular. For this reason, the demand for stable provision of high-quality printed images, even for non-skilled engineers, has increased significantly.

One of the excellent properties of the silver halide photographic light-sensitive material is that it has high sensitivity but excellent storage stability. This is because a silver halide photographic emulsion develops when only a few silver atoms are formed on its surface, and it develops naturally over a very long time such as when the storage stability is a problem. It has been thought that this is due to the fact that the speed at which silver atoms are generated and the speed at which silver atoms or their aggregates spontaneously break down can compete sufficiently. However, the stability of the silver halide photographic light-sensitive material with time is not sufficient, and the reaction speed becomes slow under the condition of a general chemical reaction at low temperature. Therefore, it is possible to store the silver halide photographic light-sensitive material in a refrigerator or the like. I've been jealous.

However, since the temperature of the light-sensitive material stored in the refrigerator is lowered immediately after it is taken out of the refrigerator, the sensitivity and gradation may change, or in extreme cases, the surface of the light-sensitive material may be changed. Condensation on the surface could cause sticking. For this reason, it may be repeated that before use, it is taken out of the refrigerator in advance to be familiar with the atmosphere of the room, and after use, it is stored again in the refrigerator.

While the inventors of the present invention have been conducting research on increasing the sensitivity of silver halide photographic emulsions containing a high concentration of silver chloride,
It was found that the sensitization method selected from selenium sensitization, tellurium sensitization, and reduction sensitization can enhance the sensitivity, but at the same time, it was found that the fog and the sensitivity fluctuate greatly due to storage over time. Although the storability is considerably improved by using a compound which is usually used as a stabilizer, the silver halide emulsion sensitized by these sensitizing methods has a small degree of stabilization by storage at low temperature, and also has a refrigerator. We found a phenomenon in which fluctuations in sensitivity and fog became particularly large when the product stored in was stored at room temperature and then returned to the refrigerator.

Regarding the selenium sensitization of silver halide emulsions containing a high concentration of silver chloride, JP-A-4-335336 discloses.
A silver halide emulsion consisting of 80 mol% or more of silver chloride contains a complex of iron, cobalt, nickel, ruthenium, rhenium, rhodium, osmium, iridium, platinum or gold having at least two cyano ligands. It is disclosed that a silver halide photographic light-sensitive material characterized by being sensitized with selenium improves reciprocity law failure characteristics, latent image stability and pressure resistance. However, there is no mention or suggestion that the above-mentioned performance fluctuation due to storage is improved when a silver halide photographic emulsion containing a specific gold compound inside the grain is used.

JP-A-4-335337 discloses that selenium-sensitized silver halide photographic emulsion is spectrally sensitized to have a spectral sensitivity maximum wavelength of 730 nm or more, thereby suppressing fluctuation in performance due to temperature. Has been done. JP-A-4-335338 discloses reciprocity law failure and latent image by sensitizing a silver halide photographic emulsion having a localized phase of 80 mol% or more of silver chloride and 10 mol% or more of silver bromide. It is disclosed that the image stability is improved. JP-A-4-335339 describes a selenium-sensitized silver halide photographic emulsion containing 90 mol% or more of silver chloride in a silver halide emulsion layer and a specific reducing agent such as aminophenol, reductone and catechol. It is disclosed that the contained silver halide photographic light-sensitive material has a high sensitivity, a small change in performance due to fluctuations in humidity during exposure, and a small increase in fog when stored for a long period of time. JP-A-4-335346 discloses a silver halide photographic light-sensitive material containing a selenium-sensitized silver halide emulsion containing 80 mol% or more of silver chloride and having a film pH of 4.0 to 6.5. It discloses that latent image stability and storage stability are improved. JP-A-4-335347 discloses that a selenium-sensitized silver halide emulsion having a silver chloride content of 80 mol% or more is spectrally sensitized with a red-sensitive sensitizing dye having a reduction potential of -1.25 V or less. It is disclosed that performance fluctuation due to temperature fluctuation can be reduced. JP 4-335348
The publication discloses that selenium-sensitized silver halide emulsion containing 90 mol% or more of silver chloride and a specific yellow coupler compound can improve the fluctuation of performance due to continuous processing. In JP-A-4-335349, a silver halide photographic light-sensitive material containing a selenium-sensitized silver halide emulsion containing 90 mol% or more of silver chloride is treated with a substantially sulfite-free color developer. It is disclosed that the occurrence of streak-like unevenness caused by continuous treatment is improved thereby. These publications neither disclose nor suggest the effect obtained when a silver halide emulsion containing a high concentration of silver chloride containing a gold compound therein is sensitized with selenium.

Regarding the tellurium sensitization technique, Japanese Patent Laid-Open No. 5-1138
No. 7 discloses that the reciprocity law failure characteristic can be improved by adding a metal or its ion to silver halide grains and chemically sensitizing it in the presence of a tellurium compound, and 70 mol% or more. The above-mentioned publication discloses an example in which iridium and rhodium are contained in a silver halide emulsion containing silver chloride, but this publication discloses a silver halide emulsion containing a high concentration of silver chloride containing a gold compound inside. There is no disclosure or suggestion of any effect obtained by sensitization or tellurium sensitization.

JP-A-4-335341 discloses that when a silver halide photographic emulsion containing 90 mol% or more of silver chloride is prepared, an iron compound and a simple substance of a sulfur group element are contained by the end of physical ripening. , High sensitivity, high contrast, and low fog characteristics are disclosed. However, in this publication, there is no disclosure or suggestion of the effect obtained when selenium-sensitized or tellurium-sensitized silver halide emulsion containing a high concentration of silver chloride containing a gold compound therein. Absent.

Regarding the reduction sensitization technique, many prior arts are known. For example, JP-A-2-136852 discloses a technique of reduction sensitization in the presence of ascorbic acid or its derivative. -21944 describes the technology of monodisperse silver halide emulsions sensitized by reduction with an ascorbic acid derivative.
Japanese Unexamined Patent Publication (Kokai) No. 3-168632 discloses a non-exposed sample with high sensitivity and low fog by the technology of a silver halide emulsion which is reduction-sensitized with ascorbic acid or a derivative thereof and has a ratio of (100) plane higher than that of (111) plane. It is disclosed that the storage stability of the is improved.
However, none of these publications discloses or suggests the effect obtained when reduction-sensitizing a silver halide emulsion containing a high concentration of silver chloride containing a gold compound therein.

International Patent WO 93/02390 describes a method for preparing silver halide photographic emulsions containing silver monovalent or trivalent gold ions in an amount of up to 3 × 10 ^-5 per mol of silver halide. It is disclosed that low fog characteristics can be obtained with sensitivity. U.S. Pat.No. 2,598,079 discloses a technique of sensitizing a silver halide photographic emulsion containing a specific palladium compound as a supersensitizer with 0.003 to 0.015 mol% of a gold compound. It is disclosed that fogging is achieved, and in the general description, the position of addition of the gold compound may be before the silver halide grain forming step, before the first ripening step or during the step.
Further, in JP-A-63-213836, high sensitivity and low fog characteristics are obtained by using a gold compound when forming tabular grains having a silver chloride content of 50 mol% or more and an aspect ratio of 5: 1 or more. Is disclosed. However, in any of the publications, nothing is disclosed about the effect obtained when selenium-sensitized or tellurium-sensitized or reduction-sensitized a silver halide emulsion containing a high concentration of silver chloride containing a gold compound therein. Neither has it been suggested.

[0015]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which is capable of rapid processing, has high sensitivity and has a small sensitivity variation with time. There is something to do. More specifically, using an emulsion containing high concentration of silver chloride, high sensitivity and stability over time,
In particular, it is an object of the present invention to provide a silver halide photographic light-sensitive material having excellent storage stability when the conditions change between low temperature conditions such as a refrigerator and temperature conditions around room temperature.

[0016]

While the inventors of the present invention earnestly researched a silver halide photographic light-sensitive material using a silver halide emulsion containing a high concentration of silver chloride, the above-mentioned problems of the present invention were In a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer thereon, the silver halide photographic emulsion comprises 95 mol% or more of silver chloride, and the above-mentioned general formula (1 ), At least one sensitizing method selected from the group consisting of selenium sensitization, tellurium sensitization and reduction sensitization, containing at least one of the gold compounds represented by the general formula (4) or the general formula (5). The present invention has been accomplished by finding out what is achieved by a silver halide photographic light-sensitive material characterized by being sensitized by.

The composition of the silver halide photographic emulsion according to the present invention is characterized in that it is a silver halide emulsion containing silver chloride in an amount of 95 mol% or more. It may have any halogen composition such as silver chlorobromide and silver chloroiodobromide, but silver chlorobromide containing substantially no silver iodide is preferable. Silver chlorobromide containing silver chloride of preferably 97 mol% or more, and more preferably 98 to 99.9 mol% is preferable.

The gold compound represented by the general formula (1) according to the present invention will be described.

In the above general formula (1), the anion group represented by X is a halide ion (eg, fluoride, chloride, bromide, iodide ion), perchlorate ion, borofluoride ion. , Sulfate ion, nitrate ion, thiocyanate ion, thiosulfate ion and the like. However, when p is 0, X represents a chloride ion, a thiocyanate ion, or a thiosulfate ion, and when q is 2 or 3, that is, when there are a plurality of Xs, they represent the same thing,
It may represent different things.

The 5- or 6-membered heterocyclic ligand represented by L is an anionic, cationic or neutral monocyclic group and is represented by the following general formula (2) or (3). Selected from those shown.

General formula (2)

[0022]

[Chemical 3]

General formula (3)

[0024]

[Chemical 4]

In the general formula (2), Y ₁ represents an oxygen atom, a sulfur atom, a selenium atom or a ═NR ₁ group, and Z ₁ , Z ₂ , Z ₃ and Z ₄ are each ═C (R ₂ ) R ₃ , = C
_{(R 3) -, = C} = W, = NR 1, -N = group, an oxygen atom,
Represents a sulfur atom or a selenium atom, and at least one of Z ₁ to Z ₄ represents a ═C═W group or a ═CHSH group,
And at least one is = NR ₁ , -N = group, oxygen atom,
Represents a sulfur atom or a selenium atom.

In the general formula (3), Y ₂ each represents an oxygen atom, a sulfur atom, a selenium atom or a ═NR ₁ group, and Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ are each = C (R ₂ )
_{R 3, = C (R 3} ) -, = C = W, = NR 1, -N = group,
Represents an oxygen atom, a sulfur atom or a selenium atom, Z ₁
To Z ₄ is at least one of = C = W group or = CHS
Represents an H group.

W represents an oxygen atom, a sulfur atom, a selenium atom or a = NR ₁ group. R ₁ is a hydrogen atom, an alkyl group,
Represents an aryl group or a heterocyclic group, R ₂ and R ₃ are each an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a hydroxyl group, a mercapto group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, Heterocyclic oxy group, heterocyclic thio group, amino group, phosphonyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, imide group, carbamoyl group, sulfamoyl group, acyl group, cyano group, acyloxy group, carbamoyl Oxy group, silyloxy group,
It represents each group such as ureido group, sulfamoylamino group, nitro group, sulfonyl group, sulfinyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group and sulfonamide group.

In the general formula (2), Y ₁ , Z ₁ , Z ₂ ,
Specific examples of the 5-membered heterocyclic group formed by Z ₃ and Z ₄ include imidazole series (for example, groups such as 2 (3H) -imidazoline, 2-imidazolinium, 2 (3H) -imidazoline, imidazolium, etc.) , Oxazoles (for example, groups such as 2 (3H) -oxazolidine, 2-oxazolinium, 2 (3H) -oxazoline, oxazolium), isoxazoles (for example, 3 (2
H) -isoxazoline, groups such as 3-isoxazolium), thiazoles (eg, groups such as 2 (3H) -thiazolidine, 2-thiazolium, 2 (3H) -thiazolin, thiazolium), isothiazoles (eg, , 3 (2H) -isothiazolin, 3-isothiazolium, etc.), selenazoles (eg, 2 (3H) -selenazolidine, selenazolium, etc.), oxazolidines (eg, 2-thio-oxazolidine-2,4dione, Groups such as 2,4-oxazolidinedione, oxazolidin-4-one, 2-oxazolidin-4-one),
Thiazolidine series (eg, 2-thio-thiazolin-2,4-dione, 2,4-thiazolidinedione, thiazolidin-4-one, 2
-Groups such as thiazolin-4-one), imidazolidines (eg 2-thioimidazolidine-2,4-dione, 2,4-imidazolidinedione, isothiazolidin-4-one, 2-imidazolidine-4- Groups such as one), selenazolidines (eg, groups such as 2-thioselenazolidine-2,4-dione, 2,4-selenazolidinedione, selenazolidin-4-one, 2-selenazolidin-4-one), Examples include groups such as triazole and tetrazole.

In the general formula (3), Y ₂ , Z ₁ ,
Specific examples of the 6-membered heterocyclic group formed by Z ₂ , Z ₃ , Z ₄ and Z ₅ include pyridine-based compounds (eg 1,2-dihydro-2-pyridylidene, 2-pyridinium, tetrahydropyridine-
Groups such as 2,4-dione and tetrahydropyridine-2,6-dione), pyrimidines (eg tetrahydropyrimidine-
2,4-dione, tetrahydropyrimidine-2,6-dione, hexahydropyridine-2,4,6-trione, 2-thio-hexahydropyridine-2,4,6-trione, etc.), pyrazoline-based (Groups such as pyrazolin-5-one and pyrazolidine-3,5-dione) and triazine.

In the groups substituting on these rings,
Examples of the alkyl group represented by R ₁ , R ₂ and R ₃ include straight chain / branched unsubstituted groups such as methyl, ethyl, propyl, amyl, 2-ethylhexyl, dodecyl, 2-hexyldecyl and octadecyl. , A cyclic group such as cyclopentyl, cyclohexyl, or 2-carboxyethyl, 2-hydroxylethyl, 2-methanesulfonylaminoethyl,
2-methoxyethyl, 2- (2-methoxyethoxy) ethyl,
Substituted groups such as 2-methanesulfonylethyl, 3-sulfopropyl, trifluoromethyl and the like can be mentioned.

In the groups substituting on these rings:
Examples of the aryl group represented by R ₁ , R ₂ and R ₃ include phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-nitrophenyl, 3-nitrophenyl, 4 -Methanesulfonylphenyl, 3-methanesulfonylaminophenyl, 2,4,6-trichlorophenyl, 4-fluorophenyl 2-methoxyphenyl, 2-acetylaminophenyl, 2-
Examples thereof include substituted and unsubstituted groups such as (2-ethylureido) phenyl.

In the groups substituting on these rings:
Examples of the heterocyclic group represented by R ₁ , R ₂ and R ₃ include 2-pyridyl, 2-furyl, 2-pyrimidyl, 2-thienyl,
Examples thereof include substituted and unsubstituted groups such as 5-nitro-2-thienyl, 4-methyl-2-thiazolyl, 1-pyridinyl and the like.

As the halogen atom represented by R ₂ and R ₃ ,
For example, fluorine, chlorine, bromine, iodine atom, the alkoxy group, for example, methoxy, ethoxy, propoxy, 2-methoxyethoxy, 2-methylthioethoxy, 2-methanesulfonylethoxy, 2-dodecyloxy, etc. substitution,
Each unsubstituted group is mentioned.

Examples of the aryloxy group represented by R ₂ and R ₃ include substituted and unsubstituted groups such as phenoxy, 2-methylphenoxy and 4-t-butylphenoxy, and the heterocyclic oxy group includes, for example, 1 Each group such as -phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy and the like can be mentioned.

Examples of the acyloxy group represented by R ₂ and R ₃ include acetoxy and butanoyloxy groups.
Examples of the carbamoyloxy group include groups such as methylcarbamoyloxy and phenylcarbamoyloxy, and examples of the silyloxy group include groups such as trimethylsilyloxy and dibutylmethylsilyloxy.

Examples of the alkylthio group represented by R ₂ and R ₃ include methylthio, octylthio, tetradecylthio, octadecylthio, 3-phenoxypropylthio and 3-
There are substituted and unsubstituted groups such as (4-t-butylphenoxy) propylthio, and examples of the arylthio group include phenylthio, 2-butoxy-5-t-octylphenylthio and 3-
Examples thereof include groups such as pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio, and examples of the heterocyclic thio group include 2-benzothiazolylthio and 2,4-diphenoxy-1,3. Examples include groups such as 2,5-triazole-6-thio and 2-pyridylthio.

Examples of the acylamino group represented by R ₂ and R ₃ include acetamide, butanamide, benzamide and the like.

Examples of the amino group represented by R ₂ and R ₃ include amino, anilino, 2-hydroxyanilino, 2-mercaptoanilino, N-acetylanilino, methylamino,
There are groups such as N, N-diethylamino.

The ureido group represented by R ₂ and R ₃ is, for example, each group such as 2-phenylureido, 2-methylureido, 2,2-dibutylureido and the like, and the sulfamoylamino group is, for example, N, N. -Dipropylsulfamoylamino, N-
Each group such as methyl-N-decylsulfamoylamino and the like can be mentioned.

Examples of the sulfonamide group represented by R ₂ and R ₃ include methanesulfonamide, butanesulfonamide, hexanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, 2-methylthio-5-hydroxybenzenesulfonamide and the like. And the alkoxycarbonylamino group includes, for example, groups such as methoxycarbonylamino and butoxycarbonylamino.

Examples of the carbamoyl group represented by R ₂ and R ₃ include N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-methoxyethyl) carbamoyl and N, N-dimethylcarbamoyl groups. To be

The sulfonyl group represented by R ₂ and R ₃ is
Examples include groups such as methanesulfonyl, butanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, and the like, examples of the sulfinyl group include groups such as ethanesulfinyl and 3-phenoxypropylsulfinyl, and examples of the phosphonyl group include phenoxy group. Each group such as phosphonyl, ethoxyphosphonyl, phenylphosphonyl and the like can be mentioned.

Examples of the alkoxycarbonyl group represented by R ₂ and R ₃ include each group such as methoxycarbonyl and butoxycarbonyl, and examples of the aryloxycarbonyl group include groups such as phenoxycarbonyl and p-anisidyl. Examples of the acyl group include acetyl group, 3-carboxypropanoyl, benzoyl, p-mercaptobenzoyl and the like.

Examples of the imide group represented by R ₂ and R ₃ include N-succinimide, N-phthalimide, 3-allylsuccinimide and the like.

[0045] The general formula (4), and in the general formula (5), R, V, W, Y represents a hydrogen atom or a substitutable group, X ^- represents an ion to offset the intramolecular charge. l represents an integer of 1 to 3 and m represents 2 or 3. However, m-1
Represents an integer of 0 to 2, and n represents the number of ions necessary to cancel the intramolecular charge.

The substitutable groups represented by R, V, W and Y in the general formulas (4) and (5) include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acylamino group, Alkylamino group, ureido group, amino group,
Represents an acyl group and a carboxyl group.

The alkyl group may be a linear, branched or cyclic alkyl group, and is preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl and isopropyl. , Butyl, t-butyl, i-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl group, sulfopropyl group and the like.

The aralkyl group includes, for example, a benzyl group, a phenethyl group and the like, the alkenyl group includes, for example, an allyl group and a 2-butenyl group, and the aryl group includes a phenyl group and a naphthyl group. These aryl groups are further substituted. It may be substituted by possible groups.

Examples of the heterocyclic group include nitrogen atom, oxygen atom,
Represents a 5 to 6 membered optionally fused heterocycle containing at least one heteroatom of a sulfur atom. The heterocycle may have a substituent such as an alkyl group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, a halogen atom (eg, fluorine, chlorine, bromine atom).

Examples of the acyl group include acetyl group and benzoyl group, examples of the acylamino group include acetylamino group and benzoylamino group, and examples of the ureido group include ureido group, methylureido group and phenylureido group. .

[0051] by X ^- as the ions to offset intramolecular charge, represented, halide ions (chloride, bromide etc.), perchloric acid ion, a hydroxide ion, p-
Toluene sulfonate ion etc. are mentioned.

Specific examples of the gold compounds represented by the general formulas (1), (4), and (5) are shown below, but the invention is not limited thereto.

[0053]

[Chemical 5]

[0054]

[Chemical 6]

[0055]

[Chemical 7]

[0056]

[Chemical 8]

The compound of the present invention can be synthesized by a known method, for example, Bull. Chem. Soc. Japan, 48 (3), 102.
4-9 (1975), J. Inorg. Nucl. Chem., 38 (1), 1-11 (1
076), Transition Met. Chem., 2 (6), 224-227 (197
7), JP-A 1-147537, U.S. Pat.
It can be synthesized according to the method described in No. 85.

The gold compound of the present invention is preferably added to the silver halide emulsion after being dissolved in water or a water-miscible solvent such as methanol, ethanol and fluoroalcohol alone or in a mixed solvent. Further, in the case of a compound which is hardly soluble in a suitable solvent, it may be added in the form of a dispersion.

The amount of the gold compound used in the present invention varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but it is usually 1 × 10 ^-4 per mol of silver halide. It is preferably from mol to 1 × 10 ⁻⁸ mol. More preferably 1 × 10 ^- is ⁵ mol to 1 × 10 ^-8 mol.

The gold compound according to the present invention may be added at a place where the gold compound is present in advance, and a silver salt and a halide salt may be mixed to perform nucleation, or the gold compound may be added after the nucleation is completed. You may add. The gold compound may be added so as to have a uniform concentration inside the silver halide grain,
You may control the addition amount so that it may become different concentration.

Above all, it is advantageous when the region of 2 to 50 nm inside from the surface of the grain at the end of growth is added during the formation of the silver halide grains and the effect of the present invention remarkably appears. More preferably 2.5 to 20 nm from the surface of the grain after growth
It is preferable to add it in the region.

The method of adding the gold compound according to the present invention includes a method of dissolving the gold compound together with a halide salt and continuously adding it over a part or the whole of the grain forming step, or a method of mixing with a silver salt solution. It is possible to use a method of continuously adding a part or all of the grain forming step, or a method of adding the silver salt and the halide salt by an independent route.

It is advantageous that the silver halide photographic emulsion according to the present invention contains a heavy metal ion in addition to the gold compound. Heavy metal ions that can be used for such purposes include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt and other Group 8 to 10 metals (IUPAC Inorganic Compound Nomenclature Revised Edition (1989)
Group) metals such as cadmium, zinc, and mercury, and ions of lead, rhenium, molybdenum, tungsten, and chromium. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable.

These metal ions can be added to the silver halide emulsion in the form of salt or complex salt. Above all, it is preferable to add it in the form of a complex salt to the emulsion because it is easily incorporated into the silver halide emulsion and the effect of the present invention becomes large.

When the heavy metal ion forms a complex, examples of the ligand include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. be able to. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

The heavy metal compounds that can be preferably used in the silver halide emulsion according to the present invention are shown below, but the present invention is not limited thereto.

(1) FeCl ₂ (2) FeCl ₃ (3) (NH ₄ ) Fe (SO ₄ ) ₂ (4) K ₃ [Fe (CN) ₆ ] (5) K ₄ [Fe (CN) ₆ ] (6) K ₂ [IrCl ₆ ] (7) K ₃ [IrCl ₆ ] (8) K ₂ [PtCl ₆ ] (9) K ₂ [Pt (SCN) ₄ ] (10) K ₂ [NiCl ₄ ] (11 ) K ₂ [PdCl ₆ ] (12) K ₃ [RdCl ₆ ] (13) CdCl ₂ (14) ZnCl ₂ (15) K ₂ [Mo (CO) ₄ (CNO) ₂ ] (16) K ₃ [Re ( CNO) ₆ ] (17) K ₃ [Mo (OCN) ₆ ] (18) K ₄ [Fe (CNO) ₆ ] (19) K ₂ [W (CO) ₄ (CNO) ₂ ] (20) K ₂ [ Cr (CO) ₄ (CN
O) ₂ ] (21) K ₄ [Ru (CNO) ₆ ] (22) K ₂ [Ni (CN) ₄ ] (23) PbCl ₂ (24) K ₃ [Co (NH ₃ ) ₆ ] (25) K ₅ [Co (CNO) ₁₁ ] (26) K ₃ [Re (CNO) ₆ ] (27) K ₄ [Os (CNO) ₆ ] (28) K ₂ [Cd (CNO) ₄ ] (29) K ₂ [ Pt (CNO) ₄ ] (30) K ₃ [IrBr ₆ ] (31) K ₂ [IrBr ₆ ] (32) Ga (NO ₃ ) _{3 In} order to contain heavy metal ions in the silver halide emulsion according to the present invention, The heavy metal compound may be added at any place in each step before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a heavy metal compound is dissolved together with a halide salt and continuously added during the whole or a part of the grain forming process, or silver bromide is locally concentrated. It is advantageous to localize it to the existing portion.

The amount of the heavy metal ions added to the silver halide emulsion is more preferably 1 × 10 ^-9 mol or more and 1 × 10 ^-2 mol or less, and particularly 1 × 10 ⁹ mol or less per 1 mol of silver halide.
^It is preferably ^-8 mol or more and 5 × 10 ^-5 mol or less.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. Also,
U.S. Pat.Nos. 4,183,756, 4,225,666, JP-A-55-26589,
Japanese Examined Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39 (19
It is also possible to prepare particles having a shape such as an octahedron, a dodecahedron, and a dodecahedron by the method described in the literature such as 73) and use them. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The grain size of the silver halide grains according to the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2. The range is to 1.0 μm. The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's “Particle Size Analysis Method” (ASTM Symposium on Light Microscopy, 94-122).
Page, 1955) or "Theory of Photographic Processes, 3rd Edition"
(Mies and James, co-authored, Chapter 2, Macmillan, 1966).

This particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
The coefficient of variation is preferably 0.22 or less, more preferably 0.12.
It is a monodisperse silver halide grain of 5 or less. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The soluble silver salt and the soluble halide salt may be reacted by any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor described in JP-A-57-92523, 57-92524, etc., published in Germany An apparatus for continuously adding and changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, and the reaction mother liquor is taken out of the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

The selenium sensitizers of the present invention include a wide variety of selenium compounds. For example, U.S. Pat.
602592, 1623499, JP-A-60-150046, JP-A-4-
The compounds described in 25832, 4-109240, 4-147250 and the like can be mentioned.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), selenoureas (eg, N, N-).
Dimethylselenourea, N, N, N'-triethylselenourea,
N, N, N′-trimethyl-N′-heptafluoroselenourea,
N, N, N′-trimethyl-N′-heptafluoropropylcarbonylselenourea, N, N, N′-trimethyl-N ′-(4-nitrophenyl) carbonylselenourea, etc., selenoketones (eg, selenacetone) , Selenoacetophenone, etc.), selenoamides (eg, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg, tri-p-triselenophosate) And a selenide (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenoketones.

Specific examples of the technique of using these selenium sensitizers are disclosed in the following patent specifications. U.S. Patent No. 1,57
4,944, 1,602,592, 1,623,499, 3,2
No. 97,446, No. 3,297,447, No. 3,320,069, No. 3,
408,196, 3,408,197, 3,442,653, and
3,420,670, 3,591,385, French Patent 2,693,
No. 038, No. 2,093,209, Japanese Patent Publication No. 52-34491, No. 52-344
No. 92, No. 53-295, No. 57-22090, JP-A-59-180536
No. 59-185330, 59-181337, 59-187338,
59-192241, 60-150046, 60-151637, 61-
246738, JP 3-4221 A, 3-24537 A, 3-111838 A
No. 3, No. 3-116132, No. 3-148648, No. 3-237450, No. 4-
No. 16838, No. 4-25832, No. 4-32831, No. 4-96059, No.
4-109240, 140738, 4-140739, 4-147250
No. 4, No. 4-149437, No. 4-184331, No. 4-190225, No. 4-
191729, 4-195035, British Patent 255846, 861984
issue. It is also disclosed in the chemical literature such as HE Spencer et al., Journal of Photographic Science, Vol. 31, pp. 158-169 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. Further, the addition method, depending on the properties of the selenium compound used, water or methanol, a method of adding by dissolving in an organic solvent such as ethanol alone or in a mixed solvent, is also disclosed in JP-A-4-140739. A method, that is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

The temperature of the chemical ripening using the selenium sensitizer in the present invention is preferably in the range of 40 to 90 ° C. More preferably, it is 45 ° C or higher and 80 ° C or lower. Also, the pH is 4-9, p
Ag is preferably in the range of 6 to 9.5.

Regarding the tellurium sensitizer and the sensitizing method according to the present invention, US Pat. Nos. 1,623,499, 3,320,069 and 3,
772,031, 3,531,289, 3,655,394, British Patents 235,211, 1,121,496, 1,295,462, 1,39
6,696, Canadian Patent No. 800,958, Japanese Patent Laid-Open No. 4-204640, and the like. Examples of useful tellurium sensitizers include:
Telluroureas, telluroamides, etc. are mentioned. The technique for using the tellurium sensitizer may be the same as the technique for using the selenium sensitizer described above.

Specific examples of compounds preferable as the selenium sensitizer and tellurium sensitizer are shown below.

[0087]

[Chemical 9]

A known method can be used for reduction sensitizing the silver halide emulsion according to the present invention. For example,
It is also possible to use a method of adding various reducing agents,
A method of aging under conditions of high silver ion concentration or a method of aging under conditions of high pH can be used.

Examples of the reducing agent used for reduction sensitization of the silver halide emulsion according to the present invention include stannous salts such as stannous chloride, boranes such as tri-t-butylamineborane, sodium sulfite, potassium sulfite and the like. It is possible to increase sulfites, reductones such as ascorbic acid, thiourea dioxide and the like. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above has excellent reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or they are added during the formation of silver halide grains to reduce and increase them simultaneously with grain formation. You may feel.

The amount of these reducing agents to be added needs to be adjusted according to the pH of the silver halide emulsion, the concentration of silver ions, etc., but is generally 10 per mol of the silver halide emulsion.
^-7 to 10 ^-2 mol is preferred.

After the reduction sensitization, a small amount of an oxidizing agent may be used to modify the reduction sensitizing nuclei or deactivate the remaining reducing agent. Examples of the compound used for such purpose include
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide solution.

The silver halide emulsion according to the present invention may be subjected to sulfur sensitization, gold sensitization, etc. in combination with selenium sensitization, tellurium sensitization and reduction sensitization as long as the effects of the present invention are not impaired. You can also

When combined with sulfur sensitization, preferred sulfur sensitizers include thiosulfate, allylthiocarbamidothiourea, allylisothiacyanate, cystine, p-toluenethiosulfonate, rhodanine, triethylthiourea, Inorganic sulfur etc. are mentioned. The addition amount of the sulfur sensitizer used in combination is preferably changed depending on the type of silver halide emulsion to be applied and the type of sensitizing method used in combination, but it is 5 × per mol of silver halide.
The range is 10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3
The range of × 10 ^-5 mol is preferable.

When gold sensitization is performed in combination, gold sensitizers that can be preferably used include various gold complexes other than gold sulfide. The general formula (1),
The compounds represented by (4) and (5) can also be preferably used. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is usually 1 × 10 6 per mol of silver halide.
It is preferably ⁻⁴ mol to 1 × 10 ⁻⁸ mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuation during storage, and preventing fog that occurs during development. Antifoggant known in
Stabilizers can be used. As an example of a compound that can be used for such a purpose, JP-A-2-146036 discloses.
The compounds represented by the general formula (II) described in the lower column of the page can be mentioned, and specific compounds thereof include (IIa-1) to (IIa-8) described on page 8 of the publication. , (II
Examples thereof include compounds b-1) to (IIb-7), and compounds such as 1- (3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds, depending on their purpose,
It is added in steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the step of chemical sensitization, and the step of preparing a coating solution. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-2 mol per mol of silver halide, and 1 × 10 ^-5 mol to 5 mol.
× 10 ^-3 mol is more preferable. In the coating liquid preparation process,
When it is added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, and 1 × 10 ^-5 mol to 1 × 10 ^-2 mol. Is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per m ² .

Compounds represented by the general formula (I) described in JP-A-4-26837 are listed as compounds which further enhance the effects of the present invention with respect to the silver halide emulsion according to the present invention. it can. Among these compounds, the publication
The compound of the general formula (IV) described in the upper left column on page 245 is preferable. Specific examples of the compound represented by formula (I) include the compounds described on pages 245 to 246 of the same publication. Among them, preferred compounds include exemplified compounds (X-26), (X-30), (X-32) and (X-37).

To incorporate these compounds into the silver halide photographic light-sensitive material of the present invention, the compound is dissolved in water or an organic solvent which is optionally miscible with water (eg, methanol, ethanol, etc.) or an organic solvent. After circumventing the solvent (which may be immiscible with water), it can be dispersed in a hydrophilic colloid and added as a solution or dispersion. The addition amount is preferably 1.0 × 10 ⁻⁴ to 1 mol, and more preferably 1.2 × 10 ⁴ per mol of silver halide.
^{-3 to} 1.0 x 10 ^-1 mol. The time of addition is from the time of preparation of the silver halide emulsion to the time of coating.
The position of addition may be any layer of the photosensitive silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer.

The addition of these compounds into the silver halide emulsion layer is a well known technique and is described, for example, in British Patent 2,
054,187, U.S. Patents 3,582,333, 3,671,248,
3,902,905, 3,522,053, JP-A-56-52743, 58
No. 28741, No. 61-87148, etc., and is intended to improve developability, prevent fog, and improve storability of raw samples. However, these publications do not mention anything about unexpected deterioration of storage stability which occurs when the conditions cyclically change between a low temperature condition and a high temperature condition, and a gold compound is incorporated inside a silver halide grain. Nothing is said about the combination with the silver halide emulsions it contains.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used, but in particular, as a dye having absorption in the visible region,
JP-A-3-251840, AI-1 to 1 described on page 308
The dye of No. 1 is preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A No. 1-280750 are preferable. It is preferable because it has characteristics, does not affect the photographic characteristics of the silver halide photographic emulsion, and does not cause contamination due to residual color. As specific examples of preferred compounds, the same publication, page 3, lower left column,
Exemplified compounds (1) to (45) listed in the lower left column on page 5
Can be mentioned.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it was spectrally sensitized to a specific region in the wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention.
BS-1 to BS-8 described on page 28 of JP 1840 can be preferably used alone or in combination. Examples of the green-sensitizing sensitizing dye include GS-1 to GS-1 described on page 28 of the same publication.
5 is preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When image exposure is performed by infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye needs to be used.
4-285950, IRS-1 to 11 described in pages 6 to 8
The above dyes are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 8 to 9 of the publication in combination with these dyes.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide or water and adding it as a solution, or as a solid dispersion. You may add.

The solid dispersion of the sensitizing dye is mechanically dispersed in a water system using a high-speed stirring type disperser at 1 μm.
In addition to the method of pulverizing and dispersing into the following fine particles, JP-A-58-1
As described in No. 05141, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in a water system under the conditions of pH 6 to 8 and 60 to 80 ° C., the surface tension described in Japanese Patent Publication No. 60-6496 is 38 dyn.
For example, a method of dispersing in the presence of a surfactant that suppresses the e / cm or less can be used.

As a dispersing device that can be used to prepare a dispersion liquid, for example, Japanese Patent Laid-Open No. 4-125631 can be used.
In addition to the high-speed stirring type disperser shown in the figure, a ball mill, a sand mill, an ultrasonic disperser, etc. may be mentioned.

Further, in using these dispersing devices, as described in JP-A-4-125632, a method such as performing a pretreatment such as dry pulverization in advance and then performing a wet dispersion may be adopted.

The coupler used in the silver halide photographic light-sensitive material according to the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a particularly typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
The general formula (C-
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in CC in pages 18 to 21 of the same specification.
Those described as -1 to CC-9 can be mentioned.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, a general formula (M
Examples thereof include couplers represented by -I) and (M-II). Specific compounds are described in MC of pages 13 to 16 of the publication.
Examples thereof include those described as -1 to MC-11. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same publication are preferable because they are excellent in the reproduction of colors from blue to purple and red and are excellent in the depiction of details.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is represented by the general formula (Y) described on page 8 of JP-A-4-114152.
The coupler represented by -I) may be mentioned. Specific compounds are described in YC-1 to YC- on pages 9 to 11 of the same publication.
Those listed as 9 can be mentioned. Among them, YC-8 and YC-described on page 11 of the same publication
No. 9 is preferable because it can reproduce a preferable yellow color.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-
11) and compounds such as the compound (A′-1) described on page 35 of the same publication can be used. Other than this, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

In the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

As the support used in the silver halide photographic light-sensitive material of the present invention, any material may be used, and polyethylene coated paper containing white pigment, baryta paper, vinyl chloride sheet, polypropylene containing white pigment are used. ,
A polyethylene terephthalate support or the like can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used for the reflective support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina,
Alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like can be mentioned. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support is preferably 10% by weight or more, more preferably 13% by weight or more as the content in the water-resistant resin layer. Is preferred, and more preferably 15% by weight or more. The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be determined according to
It can be measured by the method described in Japanese Patent No. 28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less as the coefficient of variation described in the above publication.

The silver halide photographic light-sensitive material according to the present invention may be directly or undercoated (adhesiveness of the surface of the support) after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

Further, in the silver halide photographic light-sensitive material according to the present invention, various hardeners are used for the purpose of preventing damage or dissolution of the film during processing. As these hardeners, many compounds such as epoxy compounds, aziridine compounds, acryloyl compounds, vinylsulfonyl compounds, chlorotriazine compounds are known, and the silver halide photographic light-sensitive material according to the present invention. Any known hardener can be preferably used for the above.

Among these hardeners, a carboxyl group-activated low-molecular hardener is preferred since it has a rapid effect and the strength of the obtained coating film is high. However, when these compounds are used in a silver halide photographic light-sensitive material having a high concentration of silver chloride, the sensitivity changes during storage, especially when the conditions are cyclically changed between a low temperature condition and a high temperature condition. It has been found that there is a drawback that the sensitivity fluctuation becomes large. The silver halide photographic emulsion according to the present invention has a high resistance to such deterioration of storage stability, and is capable of achieving both physical properties of the film and stabilization of photographic performance.

Examples of the carboxyl group-activating hardener include compounds of the general formulas (HI) to (H-VIII) described on pages 10 to 17 of Japanese Patent Application No. 4-4946. . Furthermore, in addition to the compounds represented by these general formulas,
JP-A-50-38540, 52-93470, 56-43353, 58
-113929 and the compounds described in U.S. Pat. No. 3,321,313 can also be mentioned. Specific examples of the carboxyl group-activating low-molecular hardener include (H-1) to (H-60) described on pages 13 to 16 of JP-A-62-286034. .

Among the carboxyl group-activating type low molecular hardeners, the compounds represented by the general formula (HI) are disclosed in JP-A-49-519.
No. 45, No. 51-59625, No. 61-9641, No. 62-262854, No.
It can be synthesized by the method disclosed in, for example, 62-264044. Similarly, the compound represented by the general formula (H-II) is described in JP-A-51-126125 and JP-A-52-48311, and the compound represented by the general formula (H-III) is disclosed in JP-A-57-44140. , Japanese Patent Publication No. 57-46538, No. 58-50669, general formula (H-IV)
The compound represented by formula (H-) is described in JP-A-52-54427.
The compounds represented by V) are disclosed in JP-A-60-225148 and 61-2402.
No. 36, a compound represented by the general formula (H-VI) is disclosed in JP-A-62-62.
-68866 and 62-68867, compounds represented by formula (H-VII) are described in JP-A-61-128241, and
The compound represented by formula (VIII) can be synthesized according to the synthesis method disclosed in JP-A-62-234152.

The amount of the carboxyl group-activating type hardener used is
It can be arbitrarily selected according to the purpose. Usually, it can be used in a proportion of 0.01 to 10% by weight based on dry gelatin. It is particularly preferably used in a proportion of 0.05 to 5% by weight.

To form a photographic image using the silver halide photographic light-sensitive material of the present invention, the image recorded on the negative is optically combined with the silver halide photographic light-sensitive material to be printed. It may be imaged and printed, or after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube) and then formed on the silver halide photographic light-sensitive material to be printed. Printing may be performed, or the scanning may be performed by changing the intensity of the laser light based on digital information and scanning.

In the case of exposure using laser light, the exposure time per pixel is not particularly limited, but the effects of the present invention are more effectively exhibited when the exposure time is 100 microseconds or less. In the case of exposure for an extremely short time, the phenomenon that the slope of the characteristic curve greatly changes at a certain density point often occurs. If the density at the boundary where the slope of the characteristic curve changes drastically due to storage, if the sample was exposed before exposure, the exposure could not be performed to obtain an appropriate density, and a pseudo image would appear on the image. The image quality is remarkably deteriorated such as a contour being generated. The silver halide photographic light-sensitive material according to the present invention suppresses changes in photographic characteristics due to storage, but it is also possible to remarkably improve stability even with respect to characteristics at exposure of 100 microseconds or less. Yes, it can be preferably used.

The exposure time per pixel is the outer edge of the light flux when the light intensity becomes 1/2 of the maximum value in the spatial change of the light flux intensity, and is parallel to the scanning line.
When the diameter of the light beam is defined as the distance between two points where the line passing through the point where the light intensity is maximum and the outer edge of the light beam intersect, the (light beam diameter) /
The exposure time per pixel is defined as (scanning speed).

A laser printer device which is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No. 55-4.
071, JP-A-59-11062, JP-A-63-197947, JP-A
2-74942, Japanese Patent Laid-Open No. 2-236538, Japanese Patent Publication No. 56-14963, Japanese Patent Publication No. 56-40822, European Wide Area Patent 77410, Electronic Communication Department Technical Report 80, No. 244, and Movie Television Technical Journal 1984. /
6 (382), pages 34-36. A semiconductor laser is also preferably used as a light source used for exposing the silver halide photographic light-sensitive material according to the present invention. Any semiconductor laser may be used as long as it has sufficient intensity at a wavelength of 720 nm or more, and gallium / arsenic / phosphorus, aluminum / gallium / arsenic, indium / gallium / arsenic / phosphorus, aluminum / Examples include gallium, arsenic, and antimony. Among them, semiconductor lasers of 750, 780, 810, 830 and 880 nm are advantageously used in terms of light intensity and handling of silver halide photosensitive materials.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4-Amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) Aniline CD-6) 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfone Amido CD-8) N, N-Dimethyl-p-phenylenediamine CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10) 4-Amino-3-methyl-N- Ethyl-N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline Color developer contains the above-mentioned color developing agent in addition to , Known developer component compounds can be added . Usually, an alkaline agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazole, a preservative, a chelating agent and the like are used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a washing process is performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed. The development processing device used for the development processing of the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is sandwiched between rollers arranged in a processing tank, and a photosensitive material may be used for the belt. It may be an endless belt method of fixing and transporting, but a processing tank is formed in a slit shape, a processing solution is supplied to the processing tank and the photosensitive material is transported, and the processing solution is atomized. Spray method,
A web method by contact with a carrier impregnated with a treatment liquid,
A method using a viscous treatment liquid can also be used.

[0132]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

Magenta coupler (M-1) 17.5 g, additive (ST-1) 7.5 g, (ST-2) 7.5 g, (ST-3)
To 7.5 g and 10.0 g of high boiling organic solvent DNP (dinonyl phthalate), 60 ml of ethyl acetate was added and dissolved.
A magenta coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing 15.0 ml of 5% surfactant (SU-1) using an ultrasonic homogenizer.

This dispersion was mixed with a silver halide emulsion (containing 8.5 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The second layer coating liquid was also prepared in the same manner as the first layer coating liquid. Further, (H-1) was added to the second layer as a hardener. As the coating aid, surfactants (SU-1), (S
U-3) was added to adjust the surface tension.

Sample 101 was prepared as described above. The layer structure is shown in Table 1 below.

[0137]

[Table 1]

[0138]

[Chemical 10]

(Preparation of green photosensitive emulsion) 2 kept at 40 ° C.
% Aqueous gelatin solution in 1 liter
Liquid) is added simultaneously while controlling pH = 6.5 and pH = 3.0,
Furthermore, the following (solution C) and (solution D) have pAg = 7.3 and pH =
Simultaneous addition was performed while controlling to 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water was added to 200 ml (Solution B) Silver nitrate 10.0 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water was added 600ml (Solution D) 300g of silver nitrate Water was added and 600ml was added, then desalting was performed using 5% aqueous solution of Demol N and 20% magnesium sulfate manufactured by Kao Atlas, and then mixed with gelatin aqueous solution on average. A monodisperse cubic emulsion (EMP-101) having a grain size of 0.43 μm, a coefficient of variation (S / R) = 0.09 and a silver chloride content of 99.0 mol% was obtained. The coefficient of variation is defined as the ratio of the standard deviation S of the particle size to the average particle size R.

A sensitizing dye (GS-1) was used in a methanol solution, and each emulsion was chemically sensitized at 60 ° C. to prepare (Em-G101).

Sodium thiosulfate 3.4 mg / mol AgX sensitizing dye (GS-1) 100 mg / mol AgX Sodium thiosulfate was added 90 seconds after the emulsion reached a predetermined temperature, and 10 minutes after the completion of chemical sensitization. The sensitizing dye was added before, and the stabilizer (STAB-1) was added at 3 × 10 ⁻⁴ mol / mol AgX at the end of the chemical sensitization.

[0143]

[Chemical 11]

Next, in the preparation of (EMP-101), the exemplified compound (I-23) was added to (D liquid) in advance (EMP-101).
102) was prepared and chemically sensitized in the same manner as (EMP-101) to obtain (Em-G102). (EMP-102) average particle size,
The coefficient of variation was the same as that of (EMP-101), and the amount of the exemplified compound (I-23) added at the time of silver halide grain formation was 5 × 10 ^-7 mol per mol of silver halide.

In the preparation of Sample 101, the silver halide emulsion was replaced with (Em-G101) to (Em-G102).
102 was prepared.

(Em-G103) and (Em-G104) were prepared in the same manner except that the additives used for chemical sensitization in the preparation of (Em-G101) and (Em-G102) were changed as follows.

Exemplified Compound (SE-1) 2.1 mg / mol AgX Sensitizing Dye (GS-1) 100 mg / mol AgX In the same manner except that the above emulsion was used in place of (Em-G101) in the preparation of Sample 101. Samples 103 and 104 were prepared.

(Em-G105) and (Em-G106) were prepared in the same manner except that the additives used for chemical sensitization in the preparation of (Em-G101) and (Em-G102) were changed as follows.

Exemplified Compound (TE-1) 4.1 mg / mol AgX Sensitizing Dye (GS-1) 100 mg / mol AgX Sample 101 was prepared in the same manner except that the above emulsion was used instead of (Em-G101). Samples 105 and 106 were prepared.

(Em-G107) and (Em-G108) were prepared in the same manner except that the additives used for chemical sensitization in the preparation of (Em-G101) and (Em-G102) were changed as follows.

Thiourea dioxide 0.5 mg / mol AgX sensitizing dye (GS-1) 100 mg / mol AgX Samples 107, 108 were prepared in the same manner except that the above emulsion was used instead of (Em-G101) in the preparation of Sample 101. Was prepared.

Four sheets of each sample were prepared, and one sheet was exposed and developed according to a conventional method. For the other three,
One is refrigerated (storage condition 1), one is 45 ° C relative humidity 40
% Atmosphere (storage condition 2), one sheet was left at 5 ° C. for 4 hours and then stored for 8 hours in an atmosphere of 45 ° C. and 40% relative humidity (storage condition 3), and this was repeated. After being left under predetermined conditions for 21 days, these samples were collectively exposed and developed according to a conventional method. The development processing conditions are as shown below.

(Processing step) Processing step Processing temperature time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Water washing 30-34 ° C. 90 seconds Drying 60-80 ° C. 60 seconds Show.

(Color developer) Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxylethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-diphosphonate disodium 1.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'- Diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to bring the total volume to 1 liter and adjust the pH to 10.60.

(Bleach-fixing solution) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 7.5 ml Water is added to bring the total volume to 1 liter. Adjust to pH = 5.7 with potassium carbonate or glacial acetic acid.

(Washing solution) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide ( 20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to make the total volume 1 liter, and pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

The magenta dye image thus obtained was measured for G density by a PDA-65 densitometer (manufactured by Konica Corp.) to measure fog and sensitivity. The sensitivity was defined as the reciprocal of the exposure dose giving a density of 0.75, and the sensitivity of the sample evaluated immediately after the sample preparation was expressed as a relative value with sample 101 being 100. Storage condition 1,
A few samples were expressed as relative values with the sensitivity of the sample evaluated immediately after preparation of each sample being 100.

For the evaluation of fog, the measured value of the fog of the sample evaluated immediately after the sample preparation was 0, and the value of the sample evaluated immediately after the preparation of each sample was 0. The relative value is shown.

The sensitivity evaluation results are shown in Table 2 below, and the fog evaluation results are shown in Table 3.

[0160]

[Table 2]

[0161]

[Table 3]

In the sample evaluated immediately after the sample preparation, it can be seen that the silver halide emulsion subjected to selenium sensitization, tellurium sensitization and reduction sensitization has a high sensitivity and serves the purpose of increasing the sensitivity. However, it can be seen that in the case of a silver halide emulsion containing no gold compound inside the grain, the emulsion selenium sensitized, tellurium sensitized and reduction sensitized greatly changes in sensitivity and fog during storage. In particular, it was found that the performance change when the storage condition was cyclically changed between the low temperature condition and the high temperature condition was the same as or slightly worse than that when the storage condition was maintained at the high temperature. It has been shown that these drawbacks are improved in a silver halide photographic emulsion containing a gold compound inside the grains, and have the characteristic of excellent storage stability while having the advantage of high sensitivity.

On the other hand, when the silver halide emulsion containing no gold compound inside the grains was sensitized with selenium, tellurium or reduction, the fog was evaluated by sulfur immediately after preparation of the emulsion. Although the fog density is almost the same as the above, it can be seen that the fog density greatly increases due to storage.
Moreover, similar to the change in sensitivity, the change when the storage condition is cyclically changed between the low temperature condition and the high temperature condition is the same or slightly worse than that when the storage condition is maintained at the high temperature. The silver halide photographic emulsion containing the compound inside the grains was improved, and it was shown to have excellent storage stability.

Next, a silver halide emulsion (EMP-101),
Using (EMP-102), various chemical sensitizers were changed to prepare samples. Sulfur sensitizer is sodium thiosulfate 1 /
Substituting 2 moles of α-sulfur and triethylthiourea for the selenium sensitizer, the exemplary compound (SE-1) was replaced with equimolar exemplary compounds (SE-2) and (SE-3) to increase tellurium. As the sensitizer, the exemplified compound (TE-1) is replaced with equimolar exemplified compounds (TE-2) and (TE-3),
For the reduction sensitizer, thiourea dioxide was replaced with equimolar L-ascorbic acid for optimum chemical sensitization. The results of the same evaluations as above are shown in Table 4 (sensitivity) and Table 5 (fogging).

[0165]

[Table 4]

[0166]

[Table 5]

As shown in Tables 4 and 5, compared with the case where the sensitizer used for chemical sensitization is a sulfur sensitizer, the selenium sensitizer, tellurium sensitizer and reduction sensitizer have higher Sensitivity is obtained. On the other hand, when these sensitizers are used, storability,
It can be seen that there is a problem that the change in sensitivity and fog is larger than expected when the temperature is changed cyclically between the low temperature condition and the high temperature condition. Only when the gold compound is used in combination with the silver halide emulsion containing the inside of the grain, it is understood that both high sensitivity and storage stability are achieved.

Example 2 In the preparation of the silver halide emulsion (EMP-102) of Example 1, the gold compound added to (D solution) was changed as shown in Tables 6 and 7, (C solution), (C solution), A silver halide emulsion was prepared in the same manner except that it was added via a route different from that of (D liquid). However, for the samples in which the heavy metal compounds (5) and (6) were contained inside the silver halide grains, the heavy metal compound was added in (C liquid). Then, (Em-G102), (Em-G104), (E
m-G106) and (Em-G108), a green-sensitive emulsion was prepared in the same manner as described above, and a sample was prepared using the emulsion.
Evaluation was carried out in the same manner as. The evaluation results of sensitivity are shown in Tables 6 and 7, and the evaluation results of fog are shown in Tables 8 and 9.
It was shown to.

[0169]

[Table 6]

[0170]

[Table 7]

[0171]

[Table 8]

[0172]

[Table 9]

In the sample using the silver halide emulsion according to the present invention, fluctuations in sensitivity during high temperature storage, rise in fog, and fluctuations in sensitivity when storage conditions cyclically changed between low temperature and high temperature conditions. , It was confirmed that both the rise of fog was suppressed. On the other hand, when the gold compound (A) having a cyano ligand is contained inside the silver halide grain,
It is not possible to obtain the effects of the present invention, and it can be seen that there is a large change in sensitivity both when stored at high temperatures and when the conditions are cyclically changed between low temperature and high temperature storage conditions.

Addition of a heavy metal compound, Exemplified Compound (6), which is well known to improve reciprocity law failure, in place of the gold compound according to the present invention had no effect on the improvement of storage stability. However, in the sample containing this compound inside the silver halide grains together with the gold compound according to the present invention, the degree of sensitization by selenium sensitization, tellurium sensitization and reduction sensitization is large, and the storage stability of the present invention is high. The improvement effect was not impaired. In addition, the reciprocity failure was evaluated separately, but the effect of improving the reciprocity failure due to the heavy metal compound was not impaired.

Example 3 Green-sensitive silver halide emulsion of Example 1 (Em-G102),
In the preparation of (Em-G104), (Em-G106) and (Em-G108), various photosensitive silver halide emulsions were prepared by replacing the sensitizing dye with the compounds shown in Table 10. Using this silver halide photographic emulsion, a silver halide photographic light-sensitive material was prepared in the same manner as in Example 1, except that the silver halide photographic emulsion was replaced, and evaluated in the same manner as in Example 1. went. The sensitivity evaluated immediately after the sample preparation was expressed as a relative value with 100 being the sample subjected to sulfur sensitization among the samples using the same sensitizing dye. The sensitivities of the samples under the storage conditions 1, 2, and 3 were expressed as relative values with the sensitivity evaluated immediately after the sample preparation as 100.

[0176]

[Table 10]

[0177]

[Chemical 12]

[0178]

[Chemical 13]

From Table 10, it is shown that, regardless of the type of sensitizing dye, variations in sensitivity due to storage under high temperature conditions and cyclic changes between low temperature conditions and high temperature conditions are suppressed. I understand.

Further, using the samples 301 to 328, color patches were prepared by laser exposure. First, the conditions for the output of laser light for obtaining color patches of five densities of 0.5, 0.75, 1.0, 1.3, and 1.6 using the stored sample of storage condition 1 are obtained, and then the sample of storage condition 3 is obtained. Was used to determine the condition for obtaining a color patch with a density of 0.75.

The laser output conditions for obtaining a color patch having a density of 0.75 were compared between the preservation sample of preservation condition 1 and the preservation sample of preservation condition 3, and the densities of the samples of preservation condition 3 were 0.5, 1.0,
The laser output conditions for four color patches of 1.3 and 1.6 were decided.

The exposure apparatus uses helium.
Cadmium laser (about 442 nm), green light source is helium-neon laser (about 544 nm), red light source is helium-neon laser (about 633 nm), infrared light source is gallium-aluminum-arsenic semiconductor laser (about
780nm, 830nm) was prepared and the optical system was assembled.

The beam of laser light was scanned and exposed on a silver halide photographic light-sensitive material conveyed at a speed of 20 mm / sec, at a main scanning speed of 160 m / sec at right angles to the conveying direction. The beam diameter at this time is about 80 μm, and the exposure time per pixel is 5
It was 00 nanoseconds.

As for the reproduction of the color patch of 0.75 density, all the samples were within 0.02 density because the conditions were readjusted, but in the patch of 1.0 density, the deviation of the density of the comparative sample was very large. (About 0.1). On the other hand, the silver halide photographic light-sensitive material according to the present invention was able to reduce the color misregistration as a whole.

From this, it was found that the effect of stabilizing the performance of the light-sensitive material provided by the present invention can be very advantageously used in the image forming method using laser light.

Example 4 In the same manner as in the preparation of Samples 101 to 104 of Example 1, halogen compounds were prepared in the same manner except that the compounds shown in Table 11 were added to the second layer so that the coating amount was 2.5 × 10 ⁻⁵ mol / m ^2. A silver halide photographic light-sensitive material was prepared. Table 11 shows the results of evaluation of changes in sensitivity using this sample in the same manner as in Example 1. The sensitivity when evaluated immediately after sample preparation is expressed as relative sensitivity with sample 101 as 100, and the sensitivity under storage conditions 1, 2, and 3 is relative sensitivity with 100 as the sensitivity evaluated immediately after preparation for the same sample. Indicated by.

[0187]

[Table 11]

[0188]

[Chemical 14]

When the compounds A, B, and C were used, the storage stability under high temperature conditions was improved even in the comparative sample, but when the temperature was changed cyclically between the low temperature condition and the high temperature condition. Has almost no effect, whereas in the silver halide photographic light-sensitive material of the present invention, the stability is further improved even when cyclically changing between a low temperature condition and a high temperature condition. It was confirmed to work. The use of these compounds is one of the preferred embodiments of the present invention. Example 5 Samples were prepared in the same manner as in the preparation of Samples 101 to 104 of Example 1, except that the hardener was changed from (H-1) to the second layer as shown in Table 12. Example 1 using this sample
Table 12 shows the results of evaluation of changes in sensitivity in the same manner as in. The sensitivity when evaluated immediately after sample preparation is sample 101.
Is expressed as a relative sensitivity, and the sensitivity under storage conditions 1, 2, and 3 is 100 times the sensitivity of the same sample evaluated immediately after preparation.
Is shown by relative sensitivity.

[0190]

[Table 12]

[0191]

[Chemical 15]

Compounds (H-2), (H-3), (H-
When 4) and (H-5) are used, there is a tendency for the sensitivity to change particularly at high temperature storage, but in the silver halide photographic light-sensitive material of the present invention, when the hardener is changed. No particular change was observed in the storage stability, and it was confirmed that the silver halide photographic emulsion according to the present invention can exhibit excellent characteristics even under such a condition that the storage stability deteriorates.

Example 6 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the constitution described below was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 601. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-4) 10.0 g, dye image stabilizer (ST-5) 6.67 g, additive (HQ-1) 0.67 g and high 60 ml of ethyl acetate was added to and dissolved in 6.67 g of boiling point organic solvent DNP. This solution was emulsified and dispersed in 220 ml of 10% gelatin aqueous solution containing 9.5 ml of 15% surfactant (SU-1) using an ultrasonic homogenizer to give yellow. A coupler dispersion was prepared. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-6) was added to the second and fourth layers, and (H-1) was added to the seventh layer.
As the coating aid, surfactants (SU-2), (SU-
3) was added to adjust the surface tension.

The layer structure is as shown in the table below.

[0196]

[Table 13]

[0197]

[Table 14]

[0198]

[Chemical 16]

[0199]

[Chemical 17]

[0200]

[Chemical 18]

[0201]

[Chemical 19]

PVP Polyvinylpyrrolidone DOP Di (2-ethylhexyl) phthalate DIDP Di (iso-decyl) phthalate (Preparation of blue-sensitive silver halide emulsion) (EMP-101) Addition time and (C liquid)
(EMP-101) except that the addition time of (D liquid) is changed
A silver halide emulsion was prepared in the same manner as in. As a result, a monodisperse cubic emulsion (EMP-60) having an average grain size of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol%.
1) got.

Next, the above emulsion (EMP-601) was chemically sensitized with the following compound at 55 ° C. for 130 minutes to obtain a blue-sensitive silver halide emulsion (Em-B601).

Exemplified Compound (SE-1) 1.1 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing Dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing Dye BS-2 1 × 10 ^-4 mol / mol AgX (Method for preparing red-sensitive silver halide emulsion) (EMP-101)
In the preparation of (solution A) and (solution B) and (C
(EMP-1 except for changing the addition time of liquid) and (D liquid)
01), the average particle size is 0.50 μm, the coefficient of variation (S /
R) = 0.08, and a monodisperse cubic emulsion (EMP-602) having a silver chloride content of 99.0 mol% was obtained.

Further, a silver halide emulsion (EMP-602)
On the other hand, the following compounds were chemically sensitized at 60 ° C. for 120 minutes to obtain a red-sensitive silver halide emulsion (Em-R601).

[0206] Preparation of Exemplified Compound (SE-1) 2.5mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 2 × 10 ^-4 mol / mol AgX (green-sensitive emulsion ) The green-sensitive emulsion is the same as in Example 1 (Em
-G103) was used.

Then, (EMP-601) and (EMP-6
(EMP-603) and (EMP-604) were prepared in the same manner as in (02) except that chloroauric acid was added to (D solution) in an amount of 5 × 10 ^-7 mol per mol of silver halide. .
In the preparation of (Em-B601) and (Em-R601), (EM
(P-601) to (EMP-603) and (EMP-602) to (EM
(Em-B602) in the same manner except that it was replaced with P-604),
(Em-R602) was prepared.

In the preparation of Sample 601, the blue-sensitive emulsion was changed from (Em-B601) to (Em-B602), the green-sensitive emulsion was changed from (Em-G103) to (Em-G104), and the red-sensitive emulsion was changed to (Em-B104). Sample 602 was prepared in the same manner except that R601) was replaced with (Em-R602).

Samples 601 and 602 were exposed through the developed Konica Color GX-400 to form a color print. Although the sample 601 had lower sensitivity than the sample 602, almost the same color print could be obtained by adjusting the printing conditions. Double-wrap this sample in a light-shielded polyethylene bag and leave it at 5 ° C for 8 hours, then 16 hours 40
This was repeated after storing in an atmosphere of 40 ° C and 40% relative humidity.
When the color print was created under the exposure condition where the color print was first created after leaving it under the predetermined conditions for 21 days, the color print which was almost satisfactory was obtained in the sample 602, but in the sample 601, the white part of the image was obtained. Was slightly darker, and the color balance was only a yellowish print.

As described above, it was possible to confirm the excellent storage stability of the silver halide photographic light-sensitive material according to the present invention even when the conditions for actual use were approached.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one silver halide photographic emulsion layer on a support, said silver halide photographic emulsion comprising 95 mol% or more of silver chloride, and grains. The following general formula (1)
It contains at least one of the gold compounds represented by (4) or (5) and is sensitized by at least one sensitizing method selected from selenium sensitization, tellurium sensitization and reduction sensitization. A silver halide photographic light-sensitive material characterized by the above. General formula (1) [YmAun (L) p (X) q] r [In formula, Y represents a hydrogen atom or a cation group. L is 5
Or 6-membered heterocyclic ligand, and X represents an anion group. However, when p is 0, X represents a chloride ion, thiocyanate ion, or thiosulfate ion, and when q is 2 or 3, they may be the same or different. m is an integer from 0 to 2, n
Is an integer of 1 or 2, p is an integer of 0 to 3, q is an integer of 1 to 3, and r is an integer of 1 to 4. ] General formula (4) General formula (5) [In the formula, R, V, W, and Y represent a hydrogen atom or a substitutable group, and X ⁻ represents an ion that cancels the intramolecular charge. l
Represents an integer of 1 to 3 and m represents 2 or 3. However, m-1
Is an integer of 0 to 2, and n is the number of ions necessary to cancel the intramolecular charge. ]