JPH05181221A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent deterioration of photographic performance, such as increase of fog and degradation of graininess with the lapse of time after manufacture without lowering sensitivity. CONSTITUTION:Silver halide grains are reduced and sensitized in the course of their growth and have chemically or physically adsorbed in an amount of >=80% into the surface of the grains a gold compound represented by the formula: [HkAum(L)nXp]q. in which L is a 5- car 6-membered heterocyclic ligand: X is an anion; k is 0, 1, or 2; m is 1 or 2; n is 1, 2; n is 1, 2, or 3; p is 0, 1, 2, or 3; and q is 1, 2, 3, or 4. A weight ratio of the gold contained in the unit area of the silver halide photographic sensitive material to the silver contained in it is controlled to >=11.0X10<-6>.

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 emulsion and a silver halide photographic light-sensitive material using the same, and more specifically, it relates to a fog when a high-sensitivity light-sensitive material is aged for a long period of time. The present invention relates to a silver halide photographic emulsion which is improved in increase and deterioration of graininess due to the increase and a silver halide photographic light-sensitive material using the same.

[0002]

BACKGROUND OF THE INVENTION In recent years, the demand for silver halide emulsions for photography has become more and more strict, and the photographic performances such as high sensitivity, excellent graininess, high sharpness, low fog density and sufficiently high optical density are becoming higher and higher. Has been made. These seemingly different requirements are almost always solved by the low fog and high sensitivity silver halide emulsion manufacturing technology.
It is no exaggeration to say that the development of a low-fog and high-sensitivity silver halide emulsion is the biggest challenge in this industry.

As a technique for increasing the sensitivity, for example, sulfur sensitization,
Chemical sensitization by selenium sensitization, gold sensitization, noble metal sensitization with iridium, platinum, etc., reduction sensitization or the like or a combination of two or more thereof is conventionally known. Of these chemical sensitizations, it is well known that reduction sensitization can be one of the most promising chemical sensitization techniques by combining gold sensitization and sulfur sensitization.

However, the sensitization center (sensitization nucleus) formed by reduction sensitization is an aggregate of a small number of silver atoms, and a silver halide photographic emulsion sensitized by reduction sensitization is thermally unstable. Therefore, it is well known in the art that there is a serious drawback that fog increases, or desensitizes and softens during storage of photographic materials.

By the way, in recent years, with the progress of various sensitizing techniques, high-sensitivity light-sensitive materials having ISO display sensitivity of 400 or 1000 or more have been put on the market, and along with these, well-known conventional materials for long-term storage of light-sensitive materials. In addition to the fog caused by heat and humidity, the increase in fog caused by the effects of so-called natural radiation (environmental radiation and cosmic rays) and the accompanying deterioration of graininess will be highlighted as a problem that cannot be ignored. Became.

This problem has been recognized in the art as one of the major problems to be solved in order to improve the image quality of high-sensitivity light-sensitive materials in the future. The fog of the high-sensitivity silver halide photographic light-sensitive material over a long period of time and the deterioration of the graininess due to the fog are caused by the inherent sensitivity of the silver halide grains, the amount of silver and gold contained in the light-sensitive material, or the potassium ion It has been reported to be dose dependent.

As a technique for preventing deterioration due to these factors, a technique for limiting the amount of gold coating, the amount of silver coating, and the weight ratio of both contained in the photosensitive material per unit area to within a specific amount, and a technique therefor are realized. As a specific measure to achieve this, a technique of removing the gold compound and / or the gold compound which is not incorporated in the silver halide grains and is not present in the binder phase around the grains (that is, free gold) is disclosed in JP-A Nos. 1-96642 and 1-96642. -9
No. 6651, No. 1-96652 and the like.

Further, Japanese Patent Laid-Open No. 2-836 discloses a technique in which potassium ions are replaced with other ions to reduce the amount within a specific amount. However, the quantity conditions disclosed in these publications are not necessarily new conditions, but are within the range of conditions generally practiced in the industry in the past, and it has been found that they are not sufficient as a countermeasure technique for the problem at hand. There is. Further, it is considered that the technique for removing free gold and / or gold compounds disclosed in the publication group is not necessarily a good measure in terms of production stability and cost. Therefore,
There was a strong demand for new countermeasure technology.

Therefore, we have focused on the gold sensitizer, which is one of the causes of deterioration of the high-sensitivity light-sensitive material over time. Conventionally, an inorganic gold complex salt is generally used as a gold sensitizer (see, for example, US Pat. No. 2,399,083). Of these, for example, chloroauric acid (chloroauric acid), potassium chloroaurate, potassium auriothiocyanate, auric trichloride and the like are currently used as generally suitable gold sensitizers.

However, these gold complex salts have a drawback that they tend to liberate gold, and part of the liberated gold forms a stronger complex with gelatin and remains in gelatin. Therefore, the performance deterioration due to the gold sensitizer is
It is considered as a problem caused by the chemical properties of the gold sensitizer.

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a high-sensitivity silver halide photographic light-sensitive material in which deterioration of photographic performance such as increase of fog and deterioration of graininess due to aging after production is improved without reducing sensitivity. To do.

[0012]

As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by the following, and have achieved the present invention.

(1) Silver halide grains which are reduction-sensitized during the growth of silver halide grains, and on the surface of the grains, in the presence of a gold compound represented by the general formula [I], A silver halide photographic emulsion comprising chemically sensitized silver halide grains. In the general formula [I] _{[H k Au m (L) n} (X) p ] _q [Formula, L is a heterocyclic ligand 5- or 6-membered, X represents an anion group. k represents an integer of 0 to 2, m represents an integer of 1 or 2, n represents an integer of 1 to 3, and p represents 0.
Represents an integer of 3 and q represents an integer of 1 to 4. ]

(2) 80% or more of the gold in the gold compound represented by the general formula [I] described in the above item 1 is present by chemical adsorption or physical adsorption on the surface of the silver halide grain. A silver halide photographic emulsion.

(3) At least one silver halide emulsion layer is provided on a support, and the emulsion layer contains the above-mentioned item 1 or 2
A silver halide photographic light-sensitive material containing the silver halide photographic emulsion according to the item 1, and the weight ratio of gold to silver (gold / silver) contained per unit area of the light-sensitive material is 1.0 ×.
A silver halide photographic light-sensitive material characterized by having a content of 10 ^-6 or more.

The present invention will be described in detail below. In the above general formula [I], the anion group represented by X is a halogen ion (eg, fluorine, chlorine, bromine, iodine ion), a perchlorate ion, a borofluoride ion, a sulfate ion, a nitrate ion, Examples include groups such as thiocyanate ion. 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 [II] or general formula [III]. Selected from

[0017]

[Chemical 1]

In the general formulas [II] and [III], Y ₁ and Y ₂ each represent an oxygen atom, a sulfur atom, a selenium atom or a ═NR ₁ group, and Z ₁ , Z ₂ , Z ₃ and Z ₄ And Z ₅ are respectively = C (R ₂ ) (R ₃ ), = C (R ₃ )-,
= C = W, = CHSH, = NR 1, -N = group, an oxygen atom, a sulfur atom or a selenium atom, at least one = C = W group or = CHSH group Z ₁ to Z _4.

W represents an oxygen atom, a sulfur atom, a selenium atom or a = NR ₁ group. R ₁ represents a hydrogen atom, an alkyl group, 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, Aryloxy group, 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,
Carbamoyloxy group, silyloxy group, ureido group,
It represents each group such as sulfamoylamino group, nitro group, sulfonyl group, sulfinyl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group and sulfonamide group.

In the general formula [I], general formula [II] and general formula [III], Y ₁ , Z ₁ , Z ₂ , Z ₃ and Z ₄
Specific examples of the 5-membered heterocyclic group formed by are pyrrole compounds (for example, 2 (1H) -pyrroline, 2-pyrrolidium,
2 (3H) -pyrroline, groups such as pyronium, imidazole series (for example, groups such as 2 (3H) -imidazoline, 2-imidazolinium, 2 (3H) -imidazoline, imidazolium, etc.), oxazole series (for example, 2 ( 3H) -oxazolidine, 2-oxazolinium, 2 (3H) -oxazoline, oxazolium, etc. groups, isoxazole-based (eg, 2 (3H) -isoxazoline, 3-isoxazolium, etc.), thiazole-based (eg, 2 (3
H) -thiazolidine, 2-thiazolium, 2 (3H)-
Groups such as thiazoline, thiazolium), isothiazoles (eg, groups such as 3 (2H) -isothiazoline, 3-isothiazolium), selenazoles (eg, 2 (3H)-
Groups such as selenazolidine and selenazolium), oxazolidine compounds (eg 2-thiooxazolidine-2,4-dione, 2,4-oxazolidinedione, oxazolidine-
Groups such as 4-one and 2-oxazolin-4-one), thiazolidine compounds (for example, 2-thiothiazolin-2,4-dione, 2,4-thiazolidinedione, thiazolidine-4-one).
On, groups such as 2-thiazolin-4-one), imidazolidine series (for example, 2-thioimidazolidine-2,4-dione, 2,4-imidazolidinedione, isothiazolidin-4-one, 2-imidazolidine -4-one and the like),
Selenazolidine series (for example, 2-thioselenazolidine-
2,4-dione, 2,4-selenazolidinedione, selenazolidin-4-one, 2-selenazolin-4-one and the like).

In the general formula [I], general formula [II] and general formula [III], Y ₂ , Z ₁ , Z ₂ , Z ₃ and Z
Specific examples of the 6-membered heterocyclic group formed by ₄ and Z ₅ include pyridine-based compounds (for example, 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,
Groups such as 6-dione, hexahydropyridine-2,4,6-trione and 2-thiohexahydropyridine-2,4,6-trione), pyrazoline type (eg pyrazoline-5)
-One, pyrazolidine-3,5-dione and the like).

In the groups substituting on these rings,
Alkyl represented by R ₁ , R ₂ and R ₃ is, for example, a straight-chain or branched unsubstituted group such as methyl, ethyl, propyl, amyl, 2-ethylhexyl, dodecyl, 2-hexyldecyl or octadecyl, Groups on the ring such as cyclopentyl and cyclohexyl, or 2-carboxyethyl, 2-hydroxyethyl, 2-methanesulfonylaminoethyl,
Substituted groups such as 2-methoxyethyl, 2- (2-methoxyethyl) ethyl, 2-methanesulfonylethyl, 3-sulfopropyl, trifluoromethyl and the like can be mentioned.

Examples of the aryl group include phenyl and 4
-T-butylphenyl, 2,4-di-t-amylphenyl, 4-nitrophenyl, 3-nitrophenyl, 4-methanesulfonylphenyl, 3-methanesulfonylaminophenyl, 2,4,6-trichlorophenyl, 4 -Substituted or unsubstituted groups such as trifluorophenyl, 2-methoxyphenyl, 2-acetylaminophenyl, and 2- (2-ethylureido) phenyl.

Examples of the heterocyclic group include 2-pyridine,
2-furyl, 2-pyrimidyl, 2-thienyl, 5-nitro-2-thienyl, 4-methyl-2-thiazolyl, 1-
Examples include substituted and unsubstituted groups such as pyridinyl.

The halogen atom represented by R ₂ and R ₃ is, for example, each atom of fluorine, chlorine, bromine and iodine, and the alkoxy group is, for example, methoxy, ethoxy, propoxy, 2-methoxyethoxy, 2-methylthioethoxy. , 2-methanesulfonylethoxy, 2-dodecyloxy and like substituted and unsubstituted groups. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy and like substituted and unsubstituted groups. Each group of is mentioned.

Examples of the heterocyclic oxy group include groups such as 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyloxy, and examples of the acyloxy group include groups such as acetoxy and butanoyloxy. Examples of the carbamoyloxy group include groups such as acylaminooxy and N-methylcarbamoyloxy, and examples of the silyloxy group include groups such as trimethylsilyloxy and dibutylmethylsilyloxy.

Examples of the alkylthio group include substituted and unsubstituted groups such as methylthio, octylthio, tetradecylthio, octadecylthio, 3-phenoxypropylthio and 3- (4-t-butylphenoxy) propylthio. Examples of the arylthio group include phenylthio, 2-butoxy-5-t-octylphenylthio and 3
Each group such as -pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio and the like can be mentioned.

Examples of the heterocyclic thio group include 2-benzothiazolylthio and 2,4-diphenoxy-1,3,5-
Examples include groups such as triazole-6-thio and 2-pyridylthio, and examples of the acylamino group include groups such as acetamide, butanamide, and benzamide.

Examples of the amino group include amino, anilino, 2-hydroxyanilino, 2-mercaptoanilino, N-acetylanilino, methylamino and N, N-diethylamino groups, and the ureido group. Is, for example, each group of 2-phenylureido, 2-methylureido, 2,2-dibutylureido and the like, and examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino and N-methyl- Each group such as N-decylsulfamoylamino and the like,

Examples of the sulfonamide group include methanesulfonamide, butanesulfonamide, hexanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, 2-methylthio-5-hydroxybenzenesulfonamide and the like. Examples of the alkoxycarbonylamino group include groups such as methoxycarbonylamino and butoxycarbonylamino.

Examples of the aryloxycarbonylamino group include groups such as phenoxycarbonylamino, and examples of the carbamoyl group include N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-methoxyethyl) carbamoyl, Each group such as N, N-dimethylcarbamoyl can be mentioned.

Examples of the sulfamoyl group include groups such as N-ethylsulfamoyl, N, N-dipropylsulfamoyl and N, N-dimethylsulfamoyl, and examples of the sulfonyl group include methanesulfonyl,
Each group such as butanesulfonyl, benzenesulfonyl, p-toluenesulfonyl and the like can be mentioned.

Examples of the sulfinyl group include ethanesulfinyl and 3-phenoxypropylsulfinyl groups, and examples of the phosphonyl group include phenoxyphosphonyl, ethoxyphosphonyl and phenylphosphonyl groups. Examples of the alkoxycarbonyl group include groups 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 and 3
Each group such as -carboxypropanoyl, benzoyl, p-mercaptobenzoyl and the like can be mentioned, and as the imide group,
For example, N-succinimide, N-phthalimide, 3-
Examples thereof include allylsuccinimide and other groups.

As the gold compound represented by the general formula [I] used in the present invention, a compound represented by the following general formula [Ia] or general formula [Ib] is preferably used. General formula [Ia] [Au _m ′ (L) _n ′ (X) _p ′] _q General formula [Ib] H _k ′ Au (L) (X)

[In both formulas, L, X and q are the same as defined in the general formula [I]. k'is 1 or 2
Is an integer, and when X is a divalent group, k ′ is 2. m'is an integer of 1 or 2, n'is an integer of 1, 2 or 3, p'is an integer of 0 or 1, and m '+
The relationship of p '= n' is satisfied.

Specific examples of the gold compound of the general formula [I] used in the present invention are shown below, but the present invention is not limited thereto. In the following examples, the charge (oxidation) state and the binding state in the chemical structure of the gold complex are not always specified.

[0038]

[Chemical 2]

[0039]

[Chemical 3]

[0040]

[Chemical 4]

[0041]

[Chemical 5]

The gold compound used in the present invention can be synthesized by a known method, for example, Bull. Chem. S
oc. Japan, 1975, 48 (3), 1024-
9, J. Inorg. nucl. Chem. , Vol.
38 (1), 7-11 (1976), Transiti
on Met. Chem. , Vol. 2 (6), 224
~ 227 (1977) and the method described in JP-A-1-147537.

The gold compound used in 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. In the case of a compound which is hardly soluble in a suitable solvent, it is preferable to add it in the form of a dispersion.

The gold compound used in the present invention can be added at any time during the emulsion production process, but it is preferable to add it at the start of chemical ripening, during or just before the end of chemical ripening. 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 is usually 1 × 10 ⁻⁴ mol to 1 mol of silver halide. It is preferably 1 × 10 ⁻⁸ mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

Further, the present invention is characterized in that 80% or more of gold of the added gold compound represented by the general formula [I] is present by chemical adsorption or physical adsorption on the surface of the silver halide grain. The average grain size of silver halide grains in the emulsion is 0.8μ
The effect is more exhibited by a silver halide emulsion having a size of m or more. The amount of gold present on the surface of the silver halide grain by chemical adsorption or physical adsorption (hereinafter referred to as being present in the silver halide grain phase) is 80% or more, preferably 85% or more, of the added amount of gold. It is more preferably 90% or more.

Here, the term "chemisorption" refers to one of the adsorption phenomena on the solid surface, which is caused by the chemical bonding force, and the heat of adsorption is usually about 20 to 100 Kcal / mol. Physical adsorption means that the cause of the adsorption phenomenon is the Van der Waals force, not the chemical bonding force,
Also known as Van der Waals adsorption. Adsorption heat is 10
It is Kcal / mol or less.

The distribution ratio of the added amount of gold to the silver halide grain phase and the binder phase can be measured by the following method. The amount of gold can be quantified by an atomic absorption method, an ICP emission spectroscopy method, a neutron activation method, a mass spectrometry method, a radioisotope tracer method, or the like. Specifically, the following processing can be performed and analyzed.

(1) In a silver halide emulsion before being coated on a support, it is divided into a silver halide grain phase and a binder phase by a centrifugation method, and the amount of gold is quantitatively determined by the above-mentioned analysis method.

(2) In the coating material coated on the support,
After swelling with water and peeling the silver halide emulsion from the support by enzymatic or acid decomposition, the silver halide phase and the binder phase are separated by a centrifugation method, and each is evaluated by the above-mentioned analysis method. ..

(3) In the coating material coated on the support,
The coated product is washed as it is with a dilute aqueous solution of sodium thiosulfate, being careful not to fix the silver halide. By this operation, the gold sensitizer in the binder phase is almost washed away, so by quantifying the amount of gold in the coating before and after the treatment with sodium thiosulfate, the amount of gold in the silver halide grain phase and the binder phase can be determined. Can be quantified.

The details of this method are described in P. A. Falens, Photographie Correspondents (Photograph).
hische Korrespondenz) 104
Vol. 137-146 (1968). However, in applying the above-mentioned analysis method to a silver halide emulsion, there is a drawback that it is difficult to say that it is a simple analysis method such as complicated pretreatment and risk of exposure.

Therefore, the fluorescent X-ray analysis method can be used more simply. In this case, the detection sensitivity is not always sufficient for the actual gold concentration contained in the light-sensitive material, and therefore the following procedure must be evaluated. The amount of gold added is 10 with respect to the amount actually used for the photosensitive material
An analytical sample is prepared by changing the amount in the order of double or 100 times. If the concentration is several ppm to several tens of ppm, sufficient analysis is possible.

The amount of gold in the silver halide grain phase and the binder phase of the prepared sample was analyzed, and the content of gold in the actual light-sensitive material was estimated from the dependence of each gold content on the amount of gold added. To do. The content at the gold concentration used in the actual light-sensitive material is measured by using the other analysis method described above, and the degree of agreement with the estimated value of is evaluated.

From the result, if the relationship between the actual gold concentration in the light-sensitive material and the gold concentration in the sample can be known, a similar silver halide emulsion system can be evaluated by fluorescent X-ray analysis. Analysis can be performed using the amount of sensitizer added. Alternatively, a method of concentrating the sample to increase the gold concentration in the sample can also be used.

During the chemical ripening in the present invention, other chemical sensitizers can be used together. For example, it is preferably used in combination with a sulfur sensitizer. The sulfur sensitizer may be selected from sulfur crystals, water-soluble sulfide salts, thiosulfates, thioureas, mercapto compounds, rhodanines and the like. Specific examples of these are described in US Pat. No. 1,574,9.
No.44, No.2,410,689, No.2,278,94
No. 7, No. 3,501,313, No. 3,656,955
, West German Patent 1,422,869, Japanese Patent Publication No. 49-
20533, 58-28568 and the like. Of these, thiosulfates, thioureas, and rhodanines are particularly preferable.

Other chemical sensitizers which can be used in the present invention include selenium described in US Pat. Nos. 3,420,670 and 3,297,447, and JP-A-50-71320. Compound, US Pat. No. 2,478,8
No. 50, No. 2,518, 698, No. 2, 521, 92
No. 5, No. 2,521,626, No. 2,419,973
Nos. 2,694,637 and 2,983,610, and the like, reducing substances such as amines and stannous salts, U.S. Pat. Nos. 2,448,060 and 2,566. Two
Examples thereof include salts of precious metals such as platinum, palladium, iridium and rhodium described in No. 45, No. 2,566,263 and the like.

Chemical ripening with the gold compound used in the present invention often gives good results in the presence of a silver halide solvent such as thiocyanates, thioethers, and tetrasubstituted thioureas. The chemical ripening with the gold compound used in the present invention can also be carried out in the presence of a chemical sensitization aid (chemical sensitization modifier). For example, compounds such as 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, guanosine and sodium p-toluenesulfinate can be used as chemical sensitization aids (chemical sensitization modifiers). it can.

A concrete example is shown in US Pat. No. 2,131,03.
No.8, No. 3,411,914, No. 3,554,757
No. 58, JP-A-58-126526 and "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (1966), 13.
8 to 143. P of emulsion during chemical ripening
Ag (logarithm of reciprocal of silver ion concentration) is 7.1 to 11.
It is preferably 0. The pH of the emulsion is 4.0 to
It is preferably 9.0. The temperature for chemical aging is 4
It is preferably 0 to 90 ° C.

The gold compound used in the present invention is a silver sulfide cluster formed by selectively adding a sulfur sensitizer slowly over a long period of time and selectively growing at a specific site on the surface of a silver halide grain. It can also be preferably used for degrading A technique for selectively growing silver sulfide clusters is described in JP-A-61-93447.

The silver halide photographic emulsion used in the light-sensitive material of the present invention may be of any halogen composition such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide or silver chloride. , P. Glafkides
By Shimmy e Physic Photographic (Ch
imie et Physique Photogra
picture) (Paul Montel, 1967)
Year); G. Fduffin
Written by: Photographic Emulsion Chem
Emissory) (The Focal Press, 1996); V. L. Gerikman (V.L.
Zelikman), etc., Making and Coating Photographic Emulsion (Mak)
ing and Coating Photograph
ic Emulsion) (The Focal Pr)
It can be adjusted using the method described in Ess Co. 1964).

That is, any method such as an acid method, a neutral method, an ammonia method, etc. may be used. As a forming method for reacting a soluble silver salt and a soluble halogen salt, a one-side mixing method, a simultaneous mixing method,
Any combination of them may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. One of the forms of the simultaneous mixing method is pA in a liquid phase in which silver halide is produced.
It is also possible to use a method of keeping g constant, that is, a so-called controlled double jet method.

The silver halide grain size distribution of the silver halide photographic emulsion used in the light-sensitive material of the present invention may be narrow or wide. The silver halide grains contained in the silver halide emulsion used in the light-sensitive material of the present invention are cubic, 8
It may have a regular shape such as a tetrahedron or a tetradecahedron, may have an irregular crystal shape such as a sphere, may have a twin plane, or may have a composite shape thereof. The structure of the silver halide crystal may be a structure having a substantially uniform composition, a core / shell type double structure, or a multiple layer structure. In the case of core / shell type silver halide grains, the inside (core part)
And a surface layer (shell portion) having different halogen compositions are preferable.

The gold compound used in the present invention can also be applied to sensitize tabular silver halide grain emulsions. Here, the tabular silver halide grains have a diameter / thickness ratio of 3 or more. The diameter of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain, and the thickness is represented by the distance between two parallel planes forming a tabular silver halide grain. Regarding the composition and structure of the tabular silver halide grains, the same as the above-mentioned silver halide grains can be said.

The silver halide crystal grains contained in the silver halide emulsion used in the light-sensitive material of the present invention may be formed by epitaxially bonding silver halide crystals having different compositions to a silver halide crystal as a base. Alternatively, it may be bonded to a compound other than silver halide such as silver thiocyanate and lead oxide. In the process of silver halide grain formation or physical ripening, a chalcogen compound such as sulfur, selenium and tellurium, a cadmium salt, a zinc salt,
A lead salt, a thallium salt, an iridium salt, or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt, an iron complex salt, or the like may be present together.

In the present invention, "reduction-sensitized during the growth of silver halide grains" means not only a production method in which reduction-sensitization is carried out while silver halide grains are growing, but also silver halide grains. Even when reduction-sensitized in the state where the grains are not grown, the reduction-sensitized silver halide grains are grown after the reduction-sensitization. That is,
It means that it was produced by a production method including a production method of growing reduction-sensitized silver halide grains.

The reduction sensitization carried out in the present invention is carried out by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion as is carried out during the growth of silver halide grains of the silver halide emulsion. Be seen. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The amount of the reducing agent added is determined by the type of reduction sensitizer, the grain size of the silver halide grains, the composition and crystal habit, the temperature of the reaction system,
Although it is preferable to change it depending on environmental conditions such as pH and pAg, for example, in the case of thiourea dioxide, as a rough guide, it is about 0.01 to 2 m per mol of silver halide.
Good results are obtained with g. In the case of ascorbic acid, it is preferably in the range of about 50 mg to 2 g per mol of silver halide.

As conditions for reduction sensitization, the temperature is about 40 to
70 ° C, time about 10-200 minutes, pH about 5-11,
The pAg is preferably in the range of about 1 to 10 (here, pA
The g value is the reciprocal of the Ag ⁺ ion concentration. ) As the water-soluble silver salt, silver nitrate is preferable. By adding water-soluble silver salt,
So-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably 1-6, preferably 2-4. The conditions such as temperature, pH and time are preferably within the above reduction sensitization condition range.

As the stabilizer of the silver halide emulsion containing the reduction-sensitized silver halide grains of the present invention, the following general stabilizers can be used.
Antioxidants disclosed in No. 82831 and / or V.I. S. Paper by Gahler [Zeitsh
lift fur Wissenschaftrich
e Photographie Bd. 63,133
(1969)] and the thiosulfonic acids described in JP-A No. 54-1019 are often used together with good results.

The addition of these compounds may be carried out at any point in the emulsion production process from crystal growth to the preparation process immediately before coating. In the present invention, two or more kinds of silver halide emulsions separately formed may be optionally mixed and used.

The weight of gold or silver contained per unit area of the light-sensitive material in the present invention means the unit area of the light-sensitive material including the photographic constituent layers including the silver halide emulsion layer coated on the support. It is the amount of gold and the amount of gold in the gold compound or the amount of silver in the silver and silver compound contained per unit. The gold and silver are preferably quantified by an atomic absorption method.

In the present invention, the object of the present invention is achieved by setting the ratio of the total amount of gold and the total amount of silver in the light-sensitive material to 1.0 × 10 ^-6 or more. A preferred range is 1.0 × 10 ^{−6 to} 5 × 10 ⁻⁵ .

The silver halide emulsion of the present invention may be spectrally sensitized with methine dyes and the like. The dye used in the present invention includes a cyanine dye, a merocyanine dye,
It includes complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

As the basic heterocyclic nucleus, any of the nuclei normally used for cyanine dyes can be applied to these dyes. Pyroline nuclei, oxazoline nuclei, thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc. A nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus. , Rhodanine nucleus, thiobarbituric acid nucleus, etc.
~ 6-membered heterocyclic nuclei can be applied.

Useful sensitizing dyes are, for example, German Patent 92
9,080, US Pat. Nos. 2,231,658 and 2,
493, 748, 2,503, 776, 2, 5
19,001, 2,912,329, 3,65
No. 5,394, No. 3,656,959, No. 3,67
2,897, 3,694,217, British Patent 1,
Nos. 242,588 and 44-14030.

These sensitizing dyes may be used alone, or may be used in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.
Typical examples thereof are US Pat. Nos. 268,545 and 2,972.
7,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,679,428, 3,70
No. 3,377, No. 3,769,301, No. 3,81
4,609, 3,837,862, British Patent 1,
344, 281, and Japanese Patent Publication No. 43-4936.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, an aminostilbene compound substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate (for example, US Pat. , 743, 5
No. 10), cadmium salt, azaindene compound and the like. Especially US Pat. No. 3,615,61
No. 3, No. 3,615, 641, No. 3,617, 295
The combinations described in Nos. 3,635,721 are most useful.

When the silver halide emulsion used in the light-sensitive material of the present invention is spectrally sensitized, the addition timing of the spectral sensitizing dye is
It may be at any stage before, during, and after the chemical sensitization, but when it is added before the chemical sensitization, good results are often obtained.

The silver halide emulsion used in the light-sensitive material of the present invention contains, for example, a polyalkylene oxide or its derivative such as an ether, ester or amine, a thioether compound or a thiomorpho compound for the purpose of increasing sensitivity, increasing contrast or promoting development. It may include phosphorus, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones and the like. For example, US Pat. Nos. 2,400,532 and 2,423,549,
Those described in Nos. 2,716,062, 3,617,280, 3,772,021, and 2,808,003 can be used.

The effect of the present invention is more remarkable when the sensitivity of the applied light-sensitive material is higher, and it is preferable to apply the effect to a color light-sensitive material having a specific photographic sensitivity of 340 or more. The specific photographic speed of the light-sensitive material as used in the present invention is determined according to the following test method according to ISO speed. (JIS
K 7614-1981)

(1) Test conditions The test is conducted in a room at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%, and the photosensitive material to be tested is left in this state for 1 hour or more before use. (2) Exposure The relative spectral energy distribution of the reference light on the exposed surface shall be as shown in Table 1.

[0083]

[Table 1]

The illuminance change on the exposure surface is performed by using an optical wedge, and the fluctuation of the spectral transmission density is 360-700 nm in any part of this optical wedge, and the area of less than 400 nm is within 10% and 400 nm or more. The area is within 5%. The exposure time is 1/100 second.

(3) Development Processing From exposure to development processing, the photosensitive material to be tested is kept at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%. The development process is completed within 30 minutes to 6 hours after exposure. The development process is performed as follows.

1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ° C 2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ° C 3. Washing with water 3 minutes 15 seconds 24-41 ° C 4. Stationary 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water 3 minutes 15 seconds 24-41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ° C 7. Dryness 50 ° C or less The composition of the treatment liquid used in each step is shown below.

[Color Developer] Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1 liter pH 10.0

[Bleach] Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water is added to 1 liter pH 6.0

[Fixing Solution] Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added to 1 liter pH 6.6

[Stabilizer] Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water was added to 1 liter

(4) Concentration measurement The concentration is expressed by log ₁₀ (Φ ₀ / Φ). Φ ₀ is an illumination light flux for density measurement, and Φ is a transmitted light flux of the measured portion. The geometric condition for density measurement is that the illumination light flux is a parallel light flux in the normal direction, and the standard is to use the total light flux transmitted as a transmitted light flux and diffused in a half space. , Correct with standard density strips. In addition, the emulsion film surface shall face the light receiving device side during measurement.

Density measurement was performed with blue, green, and red status M densities, and the spectral characteristics thereof are values shown in Table 2 as comprehensive characteristics of the light source, optical system, optical filter, and light receiving device used in the densitometer. To do so.

[0093]

[Table 2]

Note * Red slope 0.260 / nm Green slope 0.106 / nm Blue slope 0.250 / nm * Red slope 0.040 / nm Green slope 0.120 / nm Blue slope 0.220 / nm

(5) Determination of specific photographic sensitivity Using the results of processing and density measurement under the conditions (1) to (4), the specific photographic sensitivity is determined by the following procedure. Blue, green, for the minimum concentration of each of the red, respectively H _B represents an exposure amount corresponding to 0.15 higher concentrations lux · sec, H _G, and H _R. Of H _B and H _R, the one with the larger value (the one with the lower concentration) is designated as H _S. The specific photographic sensitivity S is calculated according to the following formula.

[0096]

[Equation 1]

The silver halide emulsion used in the light-sensitive material of the present invention may contain an antifoggant (Antifogant) and a stabilizer (Stabilizer). These compounds include the product licensing index, Vol. 92, p. 107, "Anti.
fogants and stablizers "
The materials described in the section can be used.

Known photographic additives can be used in the silver halide emulsion used in the light-sensitive material of the present invention. Examples of the known photographic additives include Research Disclosure RD-17643 shown in Table 3.
(December 1979) and RD-18716 (197).
The compound described in November, 9) is mentioned.

[0099]

[Table 3]

In the color development processing, the emulsion layer of the light-sensitive material of the present invention contains an aromatic primary amine developer (eg p-type).
A dye-forming coupler that forms a dye by a coupling reaction with an oxidant of a phenylenediamine derivative or an aminophenol derivative) may be used.

The dye-forming coupler is usually selected so that a dye that absorbs light in the light-sensitive spectrum of the emulsion layer is formed with respect to each emulsion layer, and a yellow dye is contained in the blue-sensitive emulsion layer. The forming coupler has a green-sensitive emulsion layer,
A magenta dye-forming coupler is used, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, the silver halide color photographic light-sensitive material may be prepared by using a method different from the above combination.

These dye-forming couplers preferably have a group called a ballast group having a carbon number of 8 or more, which makes the coupler non-diffusible, in the molecule. In addition, these dye-forming couplers are required to reduce 4 molecules of silver ions in order to form 1 molecule of dye, and thus even if they are 4 equivalents,
It may be either di-equivalent, which only needs to reduce the silver ion of the molecule.

The dye-forming coupler includes a development inhibitor, a development accelerator, a bleaching accelerator, a developer and a silver halide solvent by coupling with a colored coupler having an effect of color correction and an oxidized product of a developing agent. , Toning agents, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers which release photographically useful fragments. Of these, couplers that release a development inhibitor upon development to improve image sharpness and image graininess are called DIR couplers.

Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used.
Such a DIR coupler and a DIR compound are those in which an inhibitor is directly bonded to the coupling position, and a group in which the inhibitor is bonded to the coupling position via a divalent group and which is released by the coupling reaction. Intramolecular nucleophilic reaction,
Those which are bonded so as to release the inhibitor by an intramolecular electron transfer reaction (referred to as a timing DIR coupler and a timing DIR compound) are included.

Further, as the inhibitor, a diffusive agent after withdrawal and a less diffusive agent can be used alone or in combination depending on the application. A colorless coupler (also referred to as a competing coupler) that undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can be used in combination with the dye-forming coupler.

Known acylacetanilide type couplers can be preferably used as the yellow dye-forming coupler. Of these, benzoylacetanilide compounds and pivaloylacetanilide compounds can be advantageously used.

Specific examples of such a yellow color coupler are as follows:
For example, US Pat. Nos. 2,875,057 and 3,265,265
No. 506, No. 3,408,194, No. 3,551,1
55, 3,582,322, 3,725,07
2, 3,891,445, West German Patent 1,547,
868, West German Application Publication Nos. 2,219,917 and 2,
261,361, 2,414,006, British Patent 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Application Laid-Open Nos. 47-26133, 48-73147, 5;
0-6341, 50-87650, 50-12
No. 3342, No. 50-130442, No. 51-218
No. 27, No. 51-102636, No. 52-82424.
No. 52-115219, No. 58-95346, and the like.

As the magenta dye forming coupler, known 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazolotriazole type couplers, open chain acylacetonitrile type couplers, indazolone type couplers and the like can be used.

Specific examples of such a magenta color forming coupler include, for example, US Pat. Nos. 2,600,788 and 2,98.
No. 3,608, No. 3,062,653, No. 3,12
7,269, 3,311,476, 3,41
9,391, 3,519,429, 3,55
No. 8,319, No. 3,582,322, No. 3,61
5,506, 3,834,908, 3,89
1,445, West German Patent 1,810,464, West German Patent Application (OLS) 2,408,665, 2,41
7,945, 2,418,959, 2,42
No. 4,467, Japanese Patent Publication No. 40-6031, and Japanese Patent Laid-Open No. 49-
74027, 49-74028, 49-129.
No. 538, No. 50-60233, No. 50-15933.
No. 6, No. 51-20826, No. 51-26541,
52-42121, 52-58922, 53
Examples thereof include those described in Japanese Patent Application No. 55122 and Japanese Patent Application No. 55-110943.

As the cyan dye forming coupler, known phenol type or naphthol type couplers can be used. For example, a phenol-based coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol-based coupler formed from a 5-aminonaphthol skeleton, a 2-equivalent naphthol-based coupler into which an oxygen atom is introduced as a leaving group, and the like are represented.

Specific examples of such cyan color couplers are described in, for example, US Pat. No. 3,779,763 and JP-A-58.
-98731, 60-37557, U.S. Pat.
895,826, JP-A-60-225155, 6
0-222853, 59-185335, U.S. Pat. Nos. 3,488,193, 2,377,448, 60-2377448, and JP-A-60-23774.
53-52423, 54-48237, 56.
No. 27147, JP-B-49-11572, JP-A-6-
1-3142, 61-9652, 61-965.
No. 3, No. 61-39045, No. 61-50136,
Examples thereof include those described in Nos. 61-99141 and 61-105545.

The photographic light-sensitive material containing the silver halide emulsion of the present invention is manufactured by coating it on a support having good flatness and good dimensional stability during the manufacturing process or processing and little dimensional change. To be done. As the support in this case, for example, a cellulose nitrate film, a cellulose ester film, a polyvinyl acetal film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, glass, paper, metal, polyolefin, for example, a paper coated with polyethylene, polypropylene, or the like. Can be used. These supports can be subjected to surface treatment such as various hydrophilic treatments for the purpose of improving the adhesiveness to the photographic emulsion layer, for example, saponification treatment, corona discharge treatment, undercoating treatment, setting treatment, etc. Is processed.

The light-sensitive material containing the silver halide photographic emulsion of the present invention is, for example, Research Disclosure RD.
No. 17643, 176, pp. 20-30 (197).
It can be processed using a known photographic processing method and processing solution described in December, 8). The photographic processing method may be black-and-white photographic processing for obtaining a silver image or color photographic processing for obtaining a color image. The processing temperature applied to photographic processing is usually 18 ° C. to 50 ° C., but processing can be performed at a temperature lower than 18 ° C. or at a temperature of 50 ° C. or higher.

Examples of the photographic light-sensitive material containing the silver halide photographic emulsion of the present invention include various color and black-and-white light-sensitive materials. For example, color negative film for photography, color reversal film, color photographic paper, color positive film, color reversal photographic paper, direct positive,
It can be used as a color photographic material for heat development, silver die bridge, and the like, and a black and white photographic material for X ray photography, lith, micro, general photography, black and white photographic paper, and the like.

The present invention is particularly suitable for a high-sensitivity color light-sensitive material, but in the case of a multi-layer color light-sensitive material, a technique of changing the order of the layer arrangement to achieve both high sensitivity and high image quality, and the same color sensitivity Using a technique of further improving the graininess by forming the emulsion layer into a three-layer structure, and a technique of further improving the sensitivity by providing a high-sensitivity layer, particularly a reflective layer of fine grain silver halide under the high-sensitivity blue-sensitive layer. Is more preferable.

Among these techniques, the technique relating to the order of layer arrangement is described in US Pat. Nos. 4,184,876 and 4,12.
9,446, 4,186,016, 4,18
6,011, 4,267,264, 4,17
3,479, 4,157,917, 4,16
5,236, British Patents 1,560,965, 2,
138,962, 2,137,372, JP-A-5
9-177552, 59-180556, 59
-204038 and the like. The technique relating to the reflective layer is described in JP-A-59-160135.

[0117]

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

Example 1 First, the emulsions EM-1 and EM- used in this example are described below.
The preparation method of 2 is shown. [Preparation of octahedral silver iodobromide emulsion EM-1] Average grain size
33 μm monodisperse silver iodobromide grains (silver iodide content 2 mol
%) As a seed crystal, and an octahedral silver iodobromide emulsion was prepared by the double jet method. The temperature of the solution (G-1) is 75
144.4 ml of a seed emulsion corresponding to 0.34 mol was added while maintaining good temperature, pAg 7.8 and pH 7.0.

(Formation of Inner Nucleus) Thereafter, while maintaining the flow rate ratio of (H-1) and (S-1) at 1: 1, the accelerated flow rate (the flow rate at the end is 3.6 times the initial flow rate). ) Was added over 110 minutes.

(Formation of Outermost Shell) Subsequently, pAg10.
1, (H-2) and (S-2) while maintaining pH 6.0
Was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 60 minutes. After the particles were formed, they were washed with water by a conventional flocculation method, and the pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C, respectively. The emulsion thus obtained is an octahedral silver iodobromide grain having an average grain size of 1.0 μm (cubic equivalent), a broad distribution of 12.6% and an average silver iodide content of 10.0 mol%. Was a monodisperse emulsion containing. This emulsion is E
Let M-1.

[Preparation of octahedral silver iodobromide emulsion EM-2]
An octahedral silver iodobromide emulsion was prepared in the same manner as emulsion EM-1. However, at the start of outermost shell formation, thiourea dioxide was added to 0.
Reduction sensitization was performed by adding 1 mg / AgX mol.

(G-1) Ocein gelatin (average molecular weight 100,000) 100.0 g Compound-1 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Water 5000.0 ml Compound-1: poly Isopropylene / polyethyleneoxy / succinate sodium salt 10% ethanol solution

(H-1) Ocein gelatin 82.4 g Potassium bromide 192.4 g Potassium iodide 115.0 g With water 1030.5 ml (S-1) Silver nitrate 392.4 g With water 1030.5 ml

(H-2) Ocein gelatin 302.1 g Potassium bromide 713.4 g Potassium iodide 30.8 g Water 3776.8 ml (S-2) Silver nitrate 1050.0 g Water 3776.8 ml Ocein gelatin 278. 5g Potassium bromide 611.6g Potassium iodide 26.4g Water 3482.4ml

Next, each of the above emulsions EM-1 and EM-2 was equally divided, and 200 m of each spectral sensitizing dye (D-1, D-2, D-3) was added to each mole of silver halide.
g, ammonium thiocyanate 4 × 10 ^-4 mol, sodium thiosulfate 4.3 × 10 ^-6 mol, and a gold compound 1.2 × 10 ^-6 mol as shown in the table below, and each at 55 ° C. Optimally (sulfur + gold) sensitization. Then as a stabilizer 4-hydroxy-6-methyl-1,3,3a, 7
-850 mg of tetrazaindene was added. [Spectral sensitizing dye]

[0126]

[Chemical 6]

[0127]

[Chemical 7]

Then, 1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-t-amylphenoxyacetamide) benzamide] was used as a magenta coupler per mol of silver halide. -8 for 5-pyrazolone
0 g, as a colored magenta coupler, 1- (2,
2.5 g each of 4,6-trichlorophenyl) -4- (1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone was weighed before tricresyl. 120 g of phosphate and 240 mg of ethyl acetate were mixed and dissolved by heating, and then 5 g of sodium triisopropylnaphthalenesulfonate and 5 g of 7.
A coupler solution emulsified and dispersed in a solution of 550 ml of 5% gelatin aqueous solution was added to each of the above emulsions.

Next, as a hardener, 2-hydroxy-
After uniformly adding an appropriate amount of 4,6-dichlorotriazine sodium, each emulsion was coated with a coating silver amount of 2.0 g / m 2.
Sample Nos. 1 to 6 were obtained by coating on a triacetate support which had been subjected to undercoating so as to be ² , and drying.

As described above, one part of the prepared sample is 1
It was left to stand for a day. The other part is temperature 55 ℃, relative humidity 2
The sample was stored in a 0% atmosphere for 3 days and used as a forced deterioration sample. The other part is irradiated with γ-rays from ⁶⁰ Co at 100 mR,
The sample was used to estimate the effect of natural radiation. Each of these samples was subjected to wedge exposure by a usual method, color-developed according to the following color processing steps, and the photographic properties were compared and evaluated. The results obtained are shown in Table 4. In addition, the sensitivity in the table is 100 when the sensitivity of Comparative Sample 1 naturally left at room temperature is 100.
Was expressed as relative sensitivity.

Treatment process Treatment temperature Treatment time Color development 38 ° C. 3 minutes 15 seconds Bleaching 38 ° C. 6 minutes 30 seconds Washing 38 ° C. 3 minutes 15 seconds Fixing 38 ° C. 6 minutes 30 seconds Water washing 38 ° C. 3 minutes 15 seconds Stable Chemical composition 38 ° C. 1 minute 30 seconds Drying The composition of the processing liquid used in each processing step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-β-hydroxyethyl aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxyamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g bromide Sodium 1.3 g Nitrilotriacetic acid / 3 sodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.6 with sodium hydroxide.

[Bleach] Ethylenediaminetetraacetic acid ammonium ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and pH was adjusted with aqueous ammonia.
Adjust to 6.0.

[Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

[Stabilizing Solution] Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

[0136]

[Table 4]

As is apparent from Table 4, Emulsion E of the present invention
It can be seen that the samples 6 to 8 obtained by using M-2 and the gold compound in combination have higher sensitivity than the comparative sample and are relatively stable against heat and γ rays, that is, natural radiation.

Example 2 Sample 1 of a multilayer color photographic light-sensitive material was prepared by sequentially forming each layer having the composition shown below from the support side on an undercoated triacetyl cellulose film support. In the following examples, the addition amount in the silver halide photographic light-sensitive material represents the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye is shown by the number of moles per mole of silver.

Sample 1 (Comparative) First Layer: Antihalation Layer (HC-1) Black Colloidal Silver 0.2 UV Absorber (UV-1) 0.23 High Boiling Solvent (Oil-1) 0.18 Gelatin 1 .4

Second Layer: First Intermediate Layer (IL-1) Gelatin 1.3

Third layer: low-sensitivity red-sensitive emulsion layer (RL) Core / shell type silver iodobromide emulsion (average grain size 0.47 μm, average AgI content 8.5 mol%) 1.0 sensitizing dye ( SD-1) 1.8 × 10 ^-5 sensitizing dye (SD-2) 2.8 × 10 ^-4 sensitizing dye (SD-3) 3.0 × 10 ^-4 cyan coupler (C-1) 0. 70 Colored cyan coupler (CC-1) 0.066 DIR compound (D-1) 0.03 DIR compound (D-3) 0.01 High boiling point solvent (Oil-1) 0.64 Gelatin 1.2

Fourth Layer: Medium Sensitivity Red Sensitive Emulsion Layer (RM) Core / shell type silver iodobromide emulsion (average grain size 0.80 μm, average AgI content 9.0 mol%) 0.8 sensitizing dye ( SD-1) 2.1 × 10 ^-5 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-4 cyan coupler (C-1) 0. 28 Colored cyan coupler (CC-1) 0.027 DIR compound (D-1) 0.01 High boiling point solvent (Oil-1) 0.26 Gelatin 0.6

Fifth layer: High-sensitivity red-sensitive emulsion layer (RH) Core / shell type silver iodobromide emulsion (average grain size 1.07 μm, average AgI content 7.5 mol%) 1.7 sensitizing dye ( SD-1) 1.9 × 10 ^-5 sensitizing dye (SD-2) 1.7 × 10 ^-4 sensitizing dye (SD-3) 1.7 × 10 ^-4 cyan coupler (C-1) 0. 05 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.02 DIR compound (D-1) 0.025 High boiling point solvent (Oil-1) 0.17 Gelatin 1.2

Sixth Layer: Second Intermediate Layer (IL-2) Gelatin 0.80

Seventh Layer: Low-Sensitivity Green Sensitive Emulsion Layer (GL) Core / Shell Type Silver Iodobromide Emulsion (Average Grain Size 0.47 μm, Average AgI Content 8.5 Mole%) 1.1 Sensitizing Dye ( SD-4) 6.8 × 10 ^-5 Sensitizing dye (SD-5) 6.2 × 10 ^-4 Magenta coupler (M-1) 0.54 Magenta coupler (M-2) 0.19 Colored magenta coupler ( CM-1) 0.06 DIR compound (D-2) 0.017 DIR compound (D-3) 0.01 High boiling point solvent (Oil-2) 0.81 Gelatin 1.8

Eighth layer: Medium-speed green-sensitive emulsion layer (GM) Core / shell type silver iodobromide emulsion (average grain size 0.70 μm, average AgI content 10.5 mol%) 0.7 sensitizing dye ( SD-6) 1.9 × 10 ^-4 sensitizing dye (SD-7) 1.2 × 10 ^-4 sensitizing dye (SD-3) 1.5 × 10 ^-5 magenta coupler (M-1) 0. 07 Magenta coupler (M-2) 0.03 Colored magenta coupler (CM-1) 0.04 DIR compound (D-2) 0.018 High boiling point solvent (Oil-2) 0.30 Gelatin 0.8

Ninth layer: High-sensitivity green-sensitive emulsion layer (GH) Core / shell type silver iodobromide emulsion (average grain size 1.0 μm, average AgI content 8.0 mol%) 1.7 sensitizing dye ( SD-6) 1.2 × 10 ^-4 sensitizing dye (SD-7) 1.0 × 10 ^-4 sensitizing dye (SD-3) 3.4 × 10 ^-5 magenta coupler (M-1) 0. 09 Magenta coupler (M-3) 0.04 Colored magenta coupler (CM-1) 0.04 High boiling point solvent (Oil-2) 0.31 Gelatin 1.2

10th layer: Yellow filter layer (YC) Yellow colloidal silver 0.05 Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Oil-2) 0.13 Gelatin 0.7 Horimarin scavenger ( HS-1) 0.09 Horimarin scavenger (HS-2) 0.07

Eleventh layer: Low-sensitivity blue-sensitive emulsion layer (BL) Core / shell type silver iodobromide emulsion (average grain size 0.47 μm, average AgI content 8.5 mol%) 0.25 core / shell type Silver iodobromide emulsion (average grain size 0.80 μm, average AgI content 9.2 mol%) 0.25 sensitizing dye (SD-8) 5.2 × 10 ⁻⁴ sensitizing dye (SD-9) 1 1.9 × 10 ⁻⁵ Yellow coupler (Y-1) 0.65 Yellow coupler (Y-2) 0.24 DIR compound (D-1) 0.03 High boiling point solvent (Oil-2) 0.18 Gelatin 1. 3 Formalin Scavenger (HS-1) 0.08

Twelfth layer: High-interval blue-sensitive emulsion layer (BH) Core / shell type silver iodobromide emulsion (average grain size 1.0 μm, average AgI content 8.0 mol%) 1.0 sensitizing dye (SD-8) 1.8 × 10 ⁻⁴ Sensitizing dye (SD-9) 7.9 × 10 ⁻⁵ Yellow coupler (Y-1) 0.15 Yellow coupler (Y-2) 0.05 High boiling point solvent (Oil-2) 0.074 Gelatin 1.3 Formalin Scavenger (HS-1) 0.05 Formalin Scavenger (HS-2) 0.12

Thirteenth layer: First protective layer (Pro-1) Fine grain silver iodobromide emulsion 0.4 (average grain size 0.08 μm, AgI content 1 mol%) Ultraviolet absorber (UV-1) 07 Ultraviolet absorber (UV-2) 0.10 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.13 Formalin scavenger (HS-2) ) 0.37 gelatin 1.3

14th layer: Second protective layer (Pro-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethylmethacrylate particles (average particle size 3 μm) 0.02 Sliding agent (WAX-1) 0 .04 gelatin 0.6

In each layer, in addition to the above composition, a coating aid Su-1, a dispersion aid Su-2, a viscosity adjusting agent, a hardener H-1, H-2, a stabilizer ST-1. , Antifoggant AF-
1, AF-2 (Mw: 10,000 and Mw: 1, 10
20,000).

[0154]

[Chemical 8]

[0155]

[Chemical 9]

[0156]

[Chemical 10]

[0157]

[Chemical 11]

[Chemical 12]

[0158]

[Chemical 13]

[0159]

[Chemical 14]

[0160]

[Chemical 15]

[0161]

[Chemical 16]

In the silver halide photographic light-sensitive material constituting each of the above layers, each light-sensitive silver halide emulsion was subjected to (sulfur + gold) sensitization. At that time, as a sulfur sensitizer, thiol was used. Using sodium sulfate, as the gold sensitizer,
Gold compounds shown in Table 6 and ammonium thiocyanate were used as a chemical sensitization aid. The gold compounds as the gold sensitizers were used in the three coating amounts (A and B) shown in Table 5, respectively.
And C), the addition amount was adjusted in the chemical ripening step.

The inside of the silver halide grains contained in the silver halide emulsions of the fifth, ninth and twelfth high-sensitivity layers was subjected to reduction sensitization at the time of shell formation as in Example 1. did. One part of each sample thus prepared was prepared under normal conditions and allowed to stand for 3 days. The other part is ⁶⁰ Co
Was irradiated with 100 mR of γ-ray from the sample to prepare a sample for estimating the influence of natural radiation. Each of these samples was subjected to wedge exposure by a usual method and then color-developed according to the same color processing step as that used in Example 1 to comparatively evaluate photographic performance.

The results of the samples thus developed are shown in Table 6. In Table 6, the specific photographic speed shows a value calculated according to the above method for a sample naturally left for 3 days under normal conditions. Again 100m
As the range of increase in fog caused by the irradiation of R γ rays, the samples obtained for blue light, green light, and red light are shown.

[0165]

[Table 5]

[0166]

[Table 6]

As is clear from Table 6, in the sample using the comparative compound, when the amount of the gold compound (chloroauric acid) added was reduced and the weight ratio of Au / Ag was decreased, the increase in fog caused by γ rays was increased. Is reduced, but the photographic sensitivity is also greatly reduced. On the other hand, it can be seen that the sample using the compound according to the present invention can reduce the fog due to γ-rays without substantially impairing the photographic sensitivity.

Example 3 In the same manner as in Example 2, a multi-layer color light-sensitive material having the following compositions was prepared. First layer: antihalation layer Black colloidal silver Silver coating amount 0.2 g / m ² Gelatin 1.7 g / m ² UV-1 (ultraviolet absorber) 0.3 g / m ² CM-1 (colored coupler) 0.3 g / M ² Oil-1 (oil for dispersing UV absorber) 0.15 g / m ² Oil-2 (oil for dispersing UV absorber) 0.15 g / m ² Oil-3 (oil for dispersing colored coupler) 0.15 g / m ²

Second layer: intermediate layer Gelatin 1.2 g / m ²

Third layer: First red-sensitive emulsion layer EM-3 Silver iodobromide emulsion Silver coating amount 1.0 g / m ² EM-4 Silver iodobromide emulsion Silver coating amount 0.5 g / m ² Gelatin 1. 3 g / m ² SD-1 (sensitizing dye) 2 × 10 ⁻⁴ mol for 1 mol of silver SD-2 (sensitizing dye) 0.5 × 10 ⁻⁴ mol for 1 mol of silver SD-3 (sensitizing dye) Dye) 2 × 10 ⁻⁴ mol per mol of silver C-1 (coupler) 0.3 g / m ² C-2 (coupler) 0.07 g / m ² C-4 (coupler) 0.3 g / m ² CC -1 (colored coupler) 0.07 g / m ² D-4 (DIR coupler) 0.005 g / m ² Oil-1 (dispersion oil of C-1, C-2, CC-1, D-4) 0 0.2 g / m ²

Fourth layer: intermediate layer gelatin 0.8 g / m ²

Fifth layer: first green-sensitive emulsion layer EM-3 silver iodobromide emulsion silver coating amount 1.0 g / m ² EM-4 silver iodobromide emulsion silver coating amount 0.5 g / m ² gelatin 1. 4 g / m ² SD-4 (sensitizing dye) 6.8 × 10 ⁻⁵ mol SD-5 (sensitizing dye) to 1 mol of silver 6.2 × 10 ⁻⁴ mol SD-7 (to 1 mol of silver Sensitizing dye) 1.3 × 10 ⁻⁴ mol to 1 mol of silver SD-10 (sensitizing dye) 1.8 × 10 ⁻⁴ mol to 1 mol of silver SD-11 (sensitizing dye) to 1 mol of silver 9.2 × 10 ⁻⁵ mol M-3 (coupler) 0.15 g / m ² CM-2 (colored coupler) 0.08 g / m ² Oil-2 (dispersion oil for M-3 and CM-2) 0.23 g / m ²

Sixth Layer: Intermediate Layer Gelatin 0.80 g / m ² SC-2 0.05 g / m ² Oil-2 (SC-2 dispersion oil) 0.05 g / m ²

Seventh layer: First blue-sensitive emulsion layer EM-3 Silver iodobromide emulsion Silver coating amount 0.8 g / m ² Gelatin 0.6 g / m ² SD-12 (sensitizing dye) 1 mol of silver 3 × 10 ⁻⁴ mol SD-10 (sensitizing dye) 1 × 10 ⁻⁴ mol per mol of silver Y-1 (coupler) 0.3 g / m ² Oil-2 (oil for dispersing Y-1) 0 0.3 g / m ²

Eighth layer: intermediate layer Gelatin 0.80 g / m ² SC-2 0.05 g / m ² Oil-2 (dispersion oil for SC-2) 0.05 g / m ²

Ninth layer: Second red-sensitive emulsion layer EM-3 Silver iodobromide emulsion Silver coating amount 1.0 g / m ² EM-5 Silver iodobromide emulsion Silver coating amount 2.0 g / m ² Fine grain AgX Emulsion (average grain size 0.08 μm, AgI 2 mol% silver iodobromide) Silver coating amount 0.5 g / m ² gelatin 2.4 g / m ² SD-1 (sensitizing dye) 1. 0 × 10 ⁻⁴ mol SD-2 (sensitizing dye) 0.2 × 10 ⁻⁴ mol per mol of silver C-1 (coupler) 0.2 g / m ² C-3 (coupler) 0.05 g / m ² C-4 ^{(coupler) 0.10g / m 2 SC-2} 0.05g / m 2 oil-1 (C-1, C-3, C-4, SC-2 the dispersed oil) 0.4 g / m ²

10th layer: intermediate layer Gelatin 0.80 g / m ² SC-2 0.07 g / m ² CM-1 (colored coupler) 0.04 g / m ² Oil-2 (SC-2, CM-1 Dispersion oil) 0.25 g / m ²

Eleventh layer: Second green-sensitive emulsion layer EM-3 Silver iodobromide emulsion Silver coating amount 0.8 g / m ² EM-5 Silver iodobromide emulsion Silver coating amount 1.6 g / m ² Gelatin 1. 6 g / m ² SD-10 (sensitizing dye) 6.8 × 10 ⁻⁵ mol SD-7 (sensitizing dye) to 1 mol of silver 6.7 × 10 ⁻⁵ mol SD-11 (sensitizing dye) to 1 mol of silver Sensitizing dye) 2.1 × 10 ^-6 mol per mol of silver M-1 (coupler) 0.2 g / m ² CM-1 (colored coupler) 0.02 g / m ² Oil-4 (M-1, CM-1 dispersion oil) 0.2 g / m ²

Twelfth layer: intermediate layer Fine particle AgX emulsion (silver iodobromide having an average particle size of 0.08 μm and AgI 2 mol%) Silver coating amount 0.3 g / m ² gelatin 0.80 g / m ² SC-2 0.05 g / m ² Oil-2 (SC-2 dispersion oil) 0.05 g / m ²

Thirteenth layer: Second blue-sensitive emulsion layer EM-3 Silver iodobromide emulsion Silver coating amount 0.7 g / m ² EM-6 Silver iodobromide emulsion Silver coating amount 1.4 g / m ² Fine grain AgX Emulsion (silver iodobromide having an average particle size of 0.08 μm and AgI 2 mol%) Silver coating amount 0.1 g / m ² fine grain AgX emulsion (silver iodobromide having an average particle size of 0.3 μm and AgI 2 mol%) Silver coating amount 0.1 g / m ² Gelatin 2.1 g / m ² SD-10 (sensitizing dye) 1 mol of silver 0.4 × 10 ⁻⁴ mol SD-9 (sensitizing dye) 1 mol of silver 1.2 × 10 ⁻⁴ mol Y-1 (coupler) 0.8 g / m ² Oil-2 (dispersion oil of Y-1) 0.8 g / m ²

14th layer: First protective layer Gelatin 1.5 g / m ² UV-1 (ultraviolet absorber) 0.1 g / m ² UV-2 (ultraviolet absorber) 0.1 g / m ² HS-1 ( Formalin scavenger) 0.2 g / m ² HS-2 (formalin scavenger) 0.5 g / m ² Oil-1 (oil for dispersing UV absorber) 0.1 g / m ² Oil-3 (for dispersing UV absorber) Oil) 0.1g / m ²

Fifteenth layer: Second protective layer Gelatin 0.6 g / m ² Alkali-soluble matting agent (average particle size 2 μm) 0.12 g / m ² Polymethylmethacrylate particles (average particle size 3 μm) 0.02 g / m ² WAX-1 (slip agent) 0.04 g / m ² W-1 (antistatic agent) 0.004 g / m ²

In each layer, in addition to the above composition, a coating aid Su-1, a dispersion aid Su-2, Su-3, a hardener H.
-1, H-3, stabilizer ST-1, antifoggant AF-
1, AF-3 was added. The characteristics of the photosensitive silver iodobromide emulsion used in each of the above layers are shown in Table 7. Further, Table 8 shows coating conditions of the light-sensitive material thus obtained.

[0184]

[Table 7]

[0185]

[Table 8]

Most of the structures of the compounds used in this example are shown in Example 1, but the structural formulas of other compounds not shown therein are shown below.

[0187]

[Chemical 17]

[0188]

[Chemical 18]

[0189]

[Chemical 19]

Each of the samples manufactured as described above was processed according to the color processing process in the same manner as in Example 1 and the photographic characteristics were comparatively evaluated. The results obtained are shown in Table 9.

[0191]

[Table 9]

As is clear from Table 9, in the sample using the comparative compound, when the amount of the gold compound (chloroauric acid) added was reduced and the weight ratio of Au / Ag was reduced, the increase in fog due to γ-ray was increased. Although it is reduced, the photographic sensitivity is also greatly reduced. On the other hand, in the sample of the present invention using the gold compound represented by the general formula [I], the γ-sensitivity was hardly impaired, and
It can be seen that fogging due to lines can be reduced.

Example 4 A silver iodobromide emulsion containing 2.5 mol% of silver iodide was added at 60 ° C. and pA.
It was prepared by the double jet method while controlling g = 8 and pH = 2.0 to obtain a monodisperse cubic crystal emulsion having an average grain size of 0.5 μm. After desalting, this emulsion was divided into two, and one of them was added with a silver nitrate solution, and the temperature was 50 ° C., pAg = 3, pH =
And silver ripening was performed for 30 minutes to prepare Emulsion EM-7. The other one was Emulsion EM-8 without silver ripening.

A silver nitrate solution and a solution containing potassium bromide and potassium iodide were further added to these emulsions by the double jet method to grow 0.5 μm grains to 1.2 μm. After desalting, 1,3-diphenyl-2-thiourea was added to these emulsions in an amount of 2.0 × 10 ^-6 per mol of silver halide.
Mol, ammonium thiocyanate 2 × 10 ⁻⁴ mol, and 1.0 × 10 ⁻⁶ mol of a gold compound as shown in Table 7 was added.
Optimum (sulfur + gold) sensitization was performed at 5 ° C. Then, as a stabilizer, 4-hydroxy-6-methyl-
850 mg of 1,3,3a, 7-tetrazaindene was added.

Further, a general photographic additive such as a spreading agent, a thickening agent and a hardener is added to each of these emulsions, and then the amount of silver is 50 mg / 100 cm on the subbed polyethylene terephthalate film base. Sample No. ² was applied and dried according to a conventional method so that the sample No. 1-No. 8 was produced.

Sensitometry of these samples was performed as follows. The exposure uses a light source with a color temperature of 5400 ° K,
Exposed for 1/50 seconds through an optical wedge. The exposure amount is 3.2C. M. It was S. Develop with the developer below.
It was performed at 30 ° C. for 30 seconds.

[Developer] Anhydrous sodium sulfite 70 g Hydroquinone 10 g Boric anhydride 1 g Sodium carbonate monohydrate 20 g 1-Phenyl-3-pyrazolidone 0.35 g Sodium hydroxide 5 g 5-Methyl-benzotriazole 0.05 g Potassium bromide 5 g Glutar Aldehyde bisulfite 15 g Glacial acetic acid 8 g Water is added to make 1 liter.

The sensitometry was carried out on the sample immediately after coating at 55 ° C. and 20% R.O. H. The test was performed with the sample left for 3 days. The results obtained are shown in Table 10.

[0199]

[Table 10]

As is apparent from Table 10, Samples 2 to 4 of the present invention obtained by using the reduction-sensitized silver halide emulsion and the gold compound represented by the general formula [I] in combination are: It can be seen that the sample has higher sensitivity than the comparative sample and is stable to heat.

[0201]

INDUSTRIAL APPLICABILITY The present invention uses a reduction-sensitized silver halide emulsion and a gold compound represented by the general formula [I] in combination to increase the fog and increase the fog over time without decreasing the sensitivity. It is possible to obtain a high-sensitivity silver halide emulsion in which deterioration of graininess due to the environment is prevented. Further, especially when the weight ratio of gold to silver is 1.0 × 10 ⁻⁶ or more, the effect is further enhanced.

Claims (3)

[Claims] 1. A silver halide grain which has been subjected to reduction sensitization during the growth of a silver halide grain, and which is chemically present on the surface of the grain in the presence of a gold compound represented by the general formula [I]. A silver halide photographic emulsion comprising sensitized silver halide grains. In the general formula [I] _{[H k Au m (L) n} (X) p ] _q [Formula, L is a heterocyclic ligand 5- or 6-membered, X represents an anion group. k represents an integer of 0 to 2, m represents an integer of 1 or 2, n represents an integer of 1 to 3, and p represents 0.
Represents an integer of 3 and q represents an integer of 1 to 4. ] 2. A halogen compound characterized in that 80% or more of gold in the gold compound represented by the general formula [I] according to claim 1 is present by chemical adsorption or physical adsorption on the surface of silver halide grains. Silver halide photographic emulsion. 3. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, and the silver halide photographic emulsion according to claim 1 or 2 being contained in the emulsion layer. The weight ratio of gold to silver (gold / silver) contained in the photosensitive material per unit area is 1.0 × 1.
The silver halide photographic light-sensitive material, characterized in that at 0 ^-6.