JPH03266828A - Silver halide photographic sensitive material and production thereof - Google Patents

Abstract

PURPOSE:To suppress the increase fog of a sensitive material and the deterioration of graininess with the lapse of time by incorporating a specified gold compd. CONSTITUTION:At least one of sulfur-contg. gold compds. represented by formulae I, II is incorporated into at least one of the photographic constituent layers of a sensitive material. It is preferable that a silver halide emulsion contained in at least one of the layers is chemically aged in the presence of at least one of the gold compds. In the formulae I, II, each of V and W is H or a substitutable group, R is H or a substitutable group, X<-> is an ion compensating electric charge in the molecule, Y is H or a substitutable group, l is 1-3, m is 2 or 3 and n is the number of ions. Concrete examples of the gold sensitizers represented by the formulae I, II are compds. represented by formulae III, IV, respectively.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a silver halide photographic light-sensitive material, and in particular, increases in fog and accompanying deterioration of graininess when high-sensitivity light-sensitive materials are aged for a long period of time. It is related to technology for improving.

[Background technology]

In recent years, demands on silver halide photographic emulsions for photography have become increasingly strict, with increasingly higher standards being required for photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density, and sufficiently high optical density. ing. In most cases, these seemingly different demands can be solved by the production technology of low-fog, high-sensitivity silver halide emulsions, and the development of low-fog, high-sensitivity silver halide emulsions is the industry's greatest challenge. It is no exaggeration to say that this is a challenge.

By the way, in recent years, due to advances in various sensitization technologies, more than 1,000 ultra-high-sensitivity color photosensitive materials with Is○ indication have become commercially available. In addition to fog caused by dust and moisture, the increase in fog caused by the effects of so-called natural radiation (environmental radiation and cosmic rays) and the accompanying deterioration of graininess have come to be highlighted as problems that cannot be ignored. . This problem has come to be recognized in the industry as one of the major issues that must be solved in order to improve the image quality of high-sensitivity photosensitive materials in the future.

This fogging of high-sensitivity silver halide photographic light-sensitive materials due to long-term aging and the accompanying deterioration of graininess are caused by the inherent sensitivity of silver halide grains, the amount of silver and gold contained in the light-sensitive material, or the amount of potassium ions. It has been reported that it is dose dependent. In addition, as a countermeasure to the deterioration caused by these factors, we have developed a technology to limit the amount of gold coating, silver coating amount, and weight ratio of the two contained in the photosensitive material per area to within a specific amount, and a specific method for realizing this. As a countermeasure, a technique for removing gold (free gold)/or gold compounds that does not exist within and on the surface of silver halide grains is disclosed in JP-A-1-96642 and JP-A-1-9.
No. 6651, No. 1-96652, etc.

Further, a technique for replacing potassium ions with other ions to reduce the amount within a specific amount is disclosed in JP-A No. 2-836. However, the quantitative conditions disclosed in these patents are not necessarily new conditions, but are within the range of conditions that have been commonly practiced in the industry, and it has been found that they are not sufficient techniques to address the problems at hand. There is. Furthermore,
It is considered that the technology for removing free gold/or gold compounds disclosed in the same patents is not necessarily a good idea from the viewpoint of manufacturing stability and cost. Therefore, there has been a strong demand for new countermeasure technology.

Therefore, we focused on gold sensitizers, which are one of the causes of deterioration of high-sensitivity photosensitive materials over long periods of time. Conventionally, inorganic total complex salts have been generally used as gold sensitizers (see, for example, US Pat. No. 2,399,083). Among these, for example, chloroauric acid (chloroauric acid)
, potassium chloroaurate, potassium oliothiocyanate, ori/ctricchloride, etc., are currently commonly used as suitable gold sensitizers. However, these total acid salts have the disadvantage that gold is easily liberated, and some of the liberated gold forms a stronger complex with gelatin and remains in gelatin. Therefore,
The performance deterioration caused by the gold sensitizer is considered to be a problem caused by the chemical properties of the gold sensitizer.

[Purpose 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 in photographic performance such as increase in fog and deterioration of graininess due to aging after manufacture is improved.

[Structure of the invention]

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

That is, (1) in a silver halide photographic light-sensitive material having a photographic constituent layer on a support, at least one of the photographic constituent layers is a silver halide emulsion layer, and at least one of the photographic constituent layers includes: r represented by the following general formulas [I] and (I[)
A silver halide photographic material comprising at least one ttIL-containing organic gold compound.

(2) In the method for producing a silver halide photographic material,
The silver halide emulsion contained in at least one layer of the silver halide photographic light-sensitive material is chemically ripened in the presence of a sulfur-containing organic gold compound represented by the general formula [■] and (I[). A method for producing a 7% silver halide photographic material.

General formula [I] General formula CI+] (Xe)n In the formula, v and W are hydrogen atoms or substitutable groups (V and W may be connected to form a ring), R is a hydrogen atom or a substituent Possible groups: Xe represents an ion that cancels out intramolecular charges, Y represents a hydrogen atom or a substitutable group, Q represents an integer of 1 to 3, and m represents 2 or 3.

However, m-(2 is an integer of 0 to 2, and n represents the number of ions necessary to cancel the intramolecular charge.

The present invention will be explained in detail below.

In the above general formula [■] and (It), R, V, WY
Examples of substitutable groups represented by include a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acylamino group, an alkylamino group, a ureido group, an amino group, an acyl group, and a carboxyl group. Further, V and W may be connected to form a heterocycle.

The alkyl group may be any linear, branched, or cyclic alkyl group, preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 1-
Examples include butyl, pentyl, nclopentyl, hexyl, cyclohexyl, octyl group, and sulfoalkyl group.

Examples of aralkyl groups include benzyl and phenethyl groups; alkenyl groups include allyl and 2-butenyl groups; and aryl groups include phenyl and naphthyl groups. May be replaced.

The heterocyclic group represents a 5- to 6-membered optionally fused heterocycle containing at least one heteroatom of N, O, and S, and the heterocycle is an alkyl group having 1 to 8 carbon atoms. It may have a substituent such as a phenyl group, a hydroxy group, or a halogen atom (eg, Br, CQ, F).

Examples of the anru group include an acyl group and a benzoyl group; examples of the acylamino group include an acylamino group and a benzoylamino group; and examples of the ureido group include a ureido group, a methylureido group, and a phenylureido group.

When V and W are linked to form a heterocycle, it represents a 5- to 6-membered heterocycle containing a -C-N bond.

For example, thiazoline ring, thiazolone ring, thiazolium ring,
Examples include a pyrroline ring, a pyrrolidone ring, a pyrrolinium ring, an imidacilline ring, an imidasilone ring, and an imidazolium ring. Further, the heterocycle may have a substituent such as an alkyl group having 1 to 8 carbon atoms, a phenyl group, a hydroxy group, or a halogen atom (eg, F, CQ, Br).

Xe represents an ion that cancels out intramolecular charges. Examples of Xe include halogen ions (for example, COe and Bre ions), barchlorate, tosylate, and hydroxide ions.

Specific examples of the gold compound (gold sensitizer) represented by the general formula [, I) or CI+) are shown below, but the invention is not limited thereto.

(I-1) (I-2) (l 3) (■ 2) (I-4) (n -3) (I-5) (I[-4) (■ ■) The gold compound of the present invention Alternatively, it is preferable to dissolve it in a water-miscible solvent such as methanol, ethanol, or fluorinated alcohol alone or in a mixed solvent and add it to the silver halide grain emulsion. Further, in the case of a compound that is poorly soluble in a suitable solvent, it is preferable to add it in the form of a dispersion.

The gold compound of the present invention can be added at any time during the emulsion manufacturing process, but it is preferably added at the beginning, 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, aging conditions, etc., but is usually 1 x 1 per mole of silver halide.
The range is preferably 0-' mol to 1 x 10-' mol. More preferably, I x 10-' mol - 1 x 101 other chemical sensitizers can be used in combination during the chemical ripening in the present invention. For example, it is preferable to use it in combination with a sulfur sensitizer.Sulfur sensitizers include sulfur crystals, water-soluble sulfide salts, thiosulfates, thioureas, mercapto compounds,
It can be selected from rhodanines and the like. Specific examples of these are U.S. Pat. Nos. 1,574.944 and 2,4
No. 10,689, 2,278.

No. 947, No. 3,501,313, No. 3,656,9
No. 55, West German Patent No. 1,422.869, Special Publication No. 4
It is described in No. 9-20533, No. 58-28568, etc.

Among these, thiosulfates, thioureas and rhodanines are particularly preferred.

In the present invention, other chemical sensitizers that can be used in combination include, for example, U.S. Pat.
47, JP-A No. 50-71320, etc., U.S. Pat.
No. 518,698, No. 2,521, No. 925, No. 2,
No. 521,926, No. 2,419,973, No. 2,6
No. 94,637, US Pat. No. 2,983,610 Reducing substances such as amines and tin salts, US Pat. No. 2,448,060, US Pat.
．． Examples include salts of noble metals such as platinum, palladium, iridium, and rhodium, which are described in No. 566, No. 263, and the like.

Chemical ripening with the compounds of the present invention can be carried out using silver halide solvents,
For example, good results are often obtained when carried out in the presence of thiocyanates, thioethers, 4-substituted thioureas, and the like.

Chemical ripening with the compounds of the present invention can also be performed using chemical sensitization aids (
It can also be in the presence of a chemical sensitization modifier).

For example, 4-hydroxy-6-methyl-1.3.3a,
Compounds such as 7-tetrazaindene, guanosine, and sodium p-toluenesulfinate can be used as chemical sensitization aids (modifiers).

Specific examples include U.S. Patent Nos. 2,131,038 and 3.
No. 411914, No. 3,554,757, Japanese Unexamined Patent Publication No. 1983
No. 126526 and Duffin, "Photographic Emulsion Chemistry", Focal Press (1966), pages 138-143.

The pAg (logarithm of the reciprocal of silver ion concentration) of the emulsion during chemical ripening is preferably 7.0 to 11.0. Further, the pH of the emulsion is preferably 4.0 to 9.0. or,
The temperature for chemical ripening is preferably 40 to 90°C.

The gold compound of the present invention is used to transform silver sulfide clusters that are selectively grown and formed at specific locations on the surface of silver halide grains into effective gold-silver sulfide clusters by slowly adding a sulfur sensitizer over a long period of time. can also be preferably used. A technique for selectively growing silver sulfide clusters is described in JP-A-61-93447.

The silver halide photographic emulsion of the present invention may be of any halogen composition such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride.
afkides), Chimie et Physiqu/Re Photographic (Chimie et Physiqu
ePhotographique) (Paul Mon
Published by te1, 1967) Nizhiev Dufin (G, F
Photographic Emulsion - Chemistry by Dof f in
ulsion ChemistyXThe Focal
Press Published 196 Year 966 - El' Zierik?
7 (V, L, Zelikman) and others, Making and Coating 7 Autographic Emulsion a 7 (Making and Coating
Photographic Emulsion) (Th
e Focal Press, 196, 964. That is,
Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

Also, a method of forming particles under excess silver ions (
A so-called back mixing method) can also be used.

As one form of the simultaneous mixing method, a method of keeping I) Ag in the liquid phase in which silver norogenide is produced, ie, a so-called Chondrald double jet method, can also be used.

The silver halide grain size distribution of the silver halide photographic emulsions of the present invention may be narrow or broad.

The silver halide grains contained in the silver halide emulsion of the present invention may have a regular shape such as a cube, an octahedron, or a tetradecahedron, or may have an irregular crystal shape such as a spherical shape, or may have a twin crystal shape. It may have a surface or a composite form thereof. Further, the structure of the silver halide crystal may be a structure having a substantially uniform composition, a double-layered structure of the Fern/Fannel type, or a multilayer structure. In the case of core/shell type silver halide grains, it is preferable that the inside (core part) and the surface part (well part) have different halogen compositions.

The gold compounds of the present invention can also be applied to sensitize tabular silver halide grain emulsions. Here, tabular silver halide grains are grains having a diameter/thickness ratio of 3 or more. Furthermore, the "diameter" of a silver halide grain refers to the diameter of a circle with an area equal to the projected area of the grain, and the "thickness" is expressed as the distance between two parallel planes constituting a tabular silver halide grain. be done.

The composition and structure of the tabular silver halide grains are similar to those of the silver halide grains described above.

In the silver halide crystal grains contained in the silver halide emulsion of the present invention, silver halide having a different composition may be bonded to the mother silver halide crystal by Evita quineal bonding, and for example, silver thiocyanate, silver halide, It may be bonded with a compound other than silver halide, such as lead oxide. In addition, in the process of silver halide grain formation or physical ripening,
Calfgene compounds such as sulfur, selenium, and tellurium, cadmium salts, zinc salts, lead salts, thallium, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be coexisting.

Also, Special Publication No. 58-1410, “Journal of Photographic Science Vol. 025 (1)” by Moyser et al.
977), pages 19 to 27, reduction sensitization can also be applied to the inside of the silver halide crystal.

In the present invention, two or more silver halide emulsions formed separately may be optionally mixed and used.

The silver halide emulsion of the present invention can be spectrally sensitized with methine dyes and other dyes.
cyanine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styrene dyes, and hemioxonol dyes.

Particularly useful dyes are those belonging to the anine dyes, merocyanine dyes and complex melonanine dyes.

For these dyes, any of the 171 basic ring nuclei commonly used in cyanine dyes can be used. Namely, pyrroline nucleus, oxazo-1-non nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: These nuclei are fused with alicyclic hydrocarbon rings. : i.e., indolenine nucleus, benzindolenine nucleus,
Indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2,4 nucleus having a ketomethylene structure.
5- to 6-membered heterocyclic nuclei such as -dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, and thiobarbital acid group can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929.080;
U.S. Patent No. 2,231,658, U.S. Patent No. 2,493.748
No. 2,503゜776, No. 2,519.001, No. 2,912,329, No. 3,655゜394,
No. 3,656,959, No. 3,672,897, No. 3.694217, British Patent No. 1,242,588,
This is described in Japanese Patent Publication No. 44-14030.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
No. 68,545, 2. (No. 177,229, 3,3
No. 97,060, No. 3.522,052, No. 3,52
No. 7,641, No. 3,617,293, No. 3,628
, No. 964, No. 3,666.480, No. 3.679.
No. 428, No. 3,703.377, No. 3,769,3
No. 01, No. 3,814,609, No. 3,837,86
No. 2, British Patent No. 1,344゜281, Special Publication No. 43-4
It is described in No. 936, etc.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635.72)
1), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,743.510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613, U.S. Patent No. 3,615,
No. 641, No. 3,617,295, No. 3,635,7
The combinations described in No. 21 are particularly useful.

When spectrally sensitizing the silver halide emulsion of the present invention, the spectral sensitizing dye may be added at any stage before, during or after the start of chemical sensitization; Addition often gives good results.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the silver halide photographic emulsion of the present invention may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium. It may also contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

For example, US Patent Nos. 2,400.532 and 2,423.
No. 549, No. 2,716,062, No. 3,617,2
No. 80, No. 3,772,021, No. 3,808,003
You can use those listed in the No.

The silver halide emulsion of the present invention contains an antifoggant (Anti
foggar+t) and stabilizer
may contain. As a compound, see Product Licensing Index, Vol. 92, p. 107.
tifogants and 5 tabilizers
Those described in Section J can be used.

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include Research Disclosure No. RD-17643 (1978) shown in the table below.
(December 1979) and RD-18716 (November 1979).

Additive RD-17643RD-18716 page
Classification Page Classification 23 I [1648-Upper right 23 1V 648 Right-Upper right 29 N
+ 648- Upper right 24 V7
649-Bottom right //
//25 ■ 650
Left - Right 25 ■ 25 ~ 26 ■ 649 Right ~ 650 Left //
//4
V 26 X 651 right 26~27 n 650 right 26~27 XI 650 right 27 1! I
tt 27 nl tt 28 1VI 650 right chemical sensitizer sensitizing dye development accelerator antifoggant stabilizer color stain inhibitor image stabilizer ultraviolet absorber filter dye brightening agent hardening agent coating aid surfactant plasticizer Agent Super Agent Static Inhibitor Matting Agent The emulsion layer of the light-sensitive material according to the present invention contains an aromatic primary amine developer (for example, HAL) 22-diamine derivative, amino A dye-forming coupler that forms a dye by coupling reaction with an oxidized form of a phenol derivative (such as a phenol derivative) may also be used.

The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer.

However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

It is desirable that these dye-forming couplers have in their molecules a group called a ballast group, which has a carbon number of 8 or more and makes the coupler non-diffusive. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Pigment-forming power Fuller can be used as a development inhibitor, development accelerator, bleach accelerator, developer, silver halide solvent, and toning by coupling with a colored coupler that has a color correction effect and an oxidized form of a developing agent. agent, hardener, fogging agent, antifogging agent,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers.

In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those in which an inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and the inhibitor is bonded to the coupling position through a divalent group, and the inhibitor is bonded to the coupling position via a divalent group, and the inhibitor is bonded to the coupling position via a divalent group, and the inhibitor is bonded to the coupling position via a divalent group. intramolecular nucleophilic reaction,
Included are those in which the inhibitor is bonded such that it is released by an intramolecular electron transfer reaction or the like (referred to as timing DIR couplers and timing DIR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. Colorless couplers (also referred to as competitive couplers) that undergo force/fring reactions with oxidized aromatic primary amine developers but do not form dyes can be used in conjunction with dye-forming couplers.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875.057, U.S. Pat.
．． 408° No. 194, No. 3,551,155, No. 3,
No. 582.322, No. 3.725072, No. 3.89
No. 1,445, West German Patent No. 1,547,868, West German Patent Application No. 2,219.917, No. 2,261,361, No. 2゜414.006, British Patent Application No. 1,425,
No. 020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-2
No. 6133, No. 48-73147, No. 506341, No. 50-87650, No. 50-123342, No. 50-130442, No. 51-21827, No. 51
-102636, 52-82424, 52-1
No. 15219, No. 58-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolopenzimidazole couplers, pyrazolotriazole couplers, open chain anruacetonitrile couplers, indacylon couplers, etc. can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat.
No. 3゜062.653, No. 3,127,269, No. 3,311,476, No. 3゜419.391,
3,519.429, 3,558,319, 3582.322, 3,615.506, 3,
834.908, 3°891.445, West German Patent No. 1,810.464, West German Patent Application (OLS) 2,4
No. 08,665, No. 2,417,945, No. 2,41
No. 8,959, No. 2,424.467, Special Publication No. 1973-
No. 6031, JP-A-4974027, JP-A No. 49-740
No. 28, No. 49-129538, No. 5060233, No. 50-159336, No. 51-20826, No. 51-26541, No. 52-42121, No. 52-
No. 58922, No. 53-55122, patent application No. 55-1
Examples include those described in No. 10943.

As the dye-forming coupler, a known 7-enol or 7-tole coupler can be used. Typical examples include phenolic couplers substituted with an alkyl group, annulamino group, or ureido group, naphthol couplers formed from a delinquent aminonaphthol skeleton, and diisomeric naphthol couplers with an oxygen atom introduced as a leaving group. be done.

Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat.
No. 60-37557, U.S. Patent No. 2,895,826, U.S. Patent No. 60-225155, U.S. Patent No. 60-222853,
No. 59-185335, U.S. Patent No. 3°488, 193
No. 60-2377448, No. 53-52423, No. 54-48237, No. 56-27147, Equity No. 49-11572, Jikai No. 61-3142, No. 61-
9652-3, 61-39045, 61-50
No. 136, No. 61-99141, No. 61-10554
Examples include those described in No. 5.

The photographic material containing the silver halide emulsion of the present invention is
It is manufactured by coating on a support that has good flatness, good dimensional stability and little dimensional change during the manufacturing process or treatment. In this case, the support may be, for example, cellulose nitrate film, cellulose ester film, vinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass, paper, metal, polyolefin such as polyethylene, polypropylene, etc. A coated paper or the like can be used. These supports can be subjected to various surface treatments such as hydrophilic treatment for the purpose of improving adhesion with the photographic emulsion layer, such as saponification treatment, corona discharge treatment, subbing treatment, setting treatment, etc. processing is performed.

The photographic material containing the silver halide photographic emulsion of the present invention is
For example, Research Disclosure RD-17643
No. 176, pp. 20-30, (December 1978), known photographic processing methods and processing solutions can be used.

This photographic processing method may be black and white photographic processing to obtain a silver image or color photographic processing to obtain a color image. The processing temperature applied to photographic processing is usually 18℃ ~
Although the temperature is 50°C, the treatment can be performed at a temperature lower than 18°C or higher than 50°C.

Examples of photographic materials containing the silver halide photographic emulsion of the present invention include various color and black and white photographic materials. For example, color negative film for photography,
Color reversal film, color photographic paper, color positive film, color reversal photographic paper, direct positive use, heat development use,
Color photosensitive materials such as silver die bridges, and
It can be used for light-sensitive materials for ray photography, squirrel photography, micro photography, general photography, black and white photographic paper, and black and white photography.

The present invention is particularly suitable for high-sensitivity color light-sensitive materials, but in order to achieve both high sensitivity and high image quality, the present invention is suitable for multilayer color light-sensitive materials. It is more preferable to use a technique that further improves the graininess by forming a three-layer structure, and a technique that further improves sensitivity by providing a reflective layer such as fine grain silver halide under a high-sensitivity layer, especially a high-sensitivity blue-sensitive layer. . Among these techniques, the technique regarding the order of layer arrangement is disclosed in U.S. Pat. No. 4,184,876.
No. 129,446, No. 4,186,016, British Patent No. 1,560°965, U.S. Patent No. 4,186
．． No. 011, No. 4,267.264, No. 4.173,
No. 479, No. 4,157,917, No. 4,165,2
No. 36, British Patent No. 2,138,962, Japanese Unexamined Patent Publication No. 1983-
177552, British Patent No. 2,137,372, Japanese Patent Application Laid-open No. 59-180,556, Japanese Patent Application Publication No. 59-204038, etc. Incidentally, the technology regarding the reflective layer is described in Japanese Patent Laid-Open No. 160135/1983.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 A monodisperse core-shell type silver iodobromide emulsion (
An octahedral normal crystal, a cubic equivalent grain size of 1.2 μm, a grain size variation coefficient of 17%, an average silver iodide content of 8.2 mol%, and a high internal iodine type were prepared.

The emulsion was then divided into equal parts, each containing 170% of the spectral sensitizing dye (D-1, D-2D-3) per mole of silver halide.
mg, ammonium thiocyanate at 4 X 10-' mol, sodium thiosulfate at 3.7 X 10-' mol, and further a gold compound as shown in the table below. 10-' mol of OX was added, and each was optimally sensitized (sulfur + gold) at 55°C. Then, 850 mg of 4-hydroquine-6-methyl-1,3,3a,7-chitrazaindene was added as a stabilizer.
added.

Spectral sensitizing dye -1 -2 -3 Then, per mole of silver halide, magenta cobra -
as, 1-(2,4,6-trichlorophenyl)-3
-[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone as 80 g1 colored magenta coupler, 1-(2,4,6-triclophenyl)-4(l-naphthylazo)- 3-(2
Weigh out 2.5 g of -chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone, then 120 g of tricresyl phosphate, 1 240 m of ethyl acetate.
Then, a coupler solution emulsified and dispersed in a solution of 5 g of sodium triisopropylnaphthalene sulfonate and 550 mQ of a 7.5% aqueous gelatin solution was added to each of the above-mentioned emulsions.

Next, after uniformly adding an appropriate amount of sodium 2-hydroxy-4,6-cyclotriazine as a hardening agent, each emulsion was coated with a coating silver amount of 2.0 g/m''. Samples 1 to 6 were obtained by coating on a triacetate support and drying.

One part of the sample prepared as described above was left to stand for one day.

The other part was stored in an atmosphere of 55° C. and 20% relative humidity for 3 days to serve as a forced deterioration sample. Also, the other part is “G”
The sample was irradiated with 100 mR of gamma rays from o and used as a sample for estimating the degree of influence of natural radiation. These various samples were wedge-exposed in a conventional manner, developed in color according to the color processing steps described below, and comparatively evaluated for photographic properties.

The results are shown in Table 1. The sensitivities in the table are expressed as relative sensitivities, with the sensitivity of comparative sample 1 left naturally at room temperature as 100.

Processing process Processing temperature 38°C Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash 3 minutes 15
Fixed in seconds
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment solution used in each treatment step is as follows.

(Color developer) 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate
37.5g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide
Add 1.0 g of water to make a pH of 112, and adjust the pH to 10.6 using 1 sodium hydroxide.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0g water and make 1
c, and adjust the pH to 6.0 using aqueous ammonia.

(Fixer) Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make la, and adjust to pH 6.0 using acetic acid.

(Stabilizing liquid) Formalin (37% aqueous solution) 1.5m
Q Konidax (manufactured by Konica Corporation) 7.5
Add ml water to make 1Q.

As is clear from Table 1 above, Samples 3 to 6 using the compounds of the present invention had a lower
It is found that it is relatively stable against heat and gamma rays, that is, natural radiation.

Similar results were obtained when the emulsions of Samples 1 to 6 above were used in the green light-sensitive emulsion layer of a multilayered color light-sensitive material.

Example 2 An emulsion consisting of tabular grains was prepared by the same double die/to method as in Example 1. The average legality content of the emulsion grains is 10
．． 0 mol% (internal high iodine type), cubic equivalent particle size is 1.2
μm, particle size variation coefficient was 24%, and diameter/thickness ratio was 4.0.

Next, using this emulsion, a gold compound was comparatively evaluated in the same manner as in Example 1. However, as the sulfur sensitizer, toluene-3-(2-thiazolyl)thiourea was used instead of sodium periosulfate. The results are shown in Table 2, and the comparative compounds are the same as in Example 1. Further, the sensitivity of sample 7 was set as 100, and the others were expressed relatively.

As is clear from Table 2 above, Samples 9 to 12 using the compounds of the present invention are more stable against heat and gamma rays than Samples 7.8 using comparative compounds.

Example 3 A core-shell type (internal high iodine type) tetradecahedral grain emulsion containing 2 mol % of silver iodide (average cubic grain size 1.0 μm 1 grain size variation coefficient 18%) in the same manner as Example 1 was prepared.

The emulsion was then divided into equal parts, each containing 44 x 1 O-6 mol of sodium thiosulfate and 1.2 x 10-3 mol of ammonium thionate per mol of silver halide, Table 3.
Add 1.2X 10-' mol of the gold compound shown in and heat at 55°C.
Optimal sensitization (sulfur + gold) was applied to each.

After chemical ripening, each emulsion contains 4-hydroquine-6 as a stabilizer.
-Methyl-1,3,3a,7-chitrazaindene, saponin as a coating aid, and appropriate amounts of 2,4-dichloro-6-hydroquine-s-triazine as a hardening agent were added.

Each of the obtained emulsions was coated on a subbed polyester support and dried to obtain Samples 13 to 17.

A portion of the sample prepared as described above was left to stand for one day. The other part was stored in an atmosphere of 55° C. and 20% relative humidity for 3 days to serve as a forced deterioration sample. Also, the other part is”
γ-rays from Co were irradiated at 100 mR.

These samples were exposed to light (1150 seconds) using a conventional sensitometric wedge, then developed with the following processing solution at 35°C for 30 seconds, fixed, washed with water, dried, and photographically developed ( Measure the sensitivity (sensitivity and fog).

In addition, photographic sensitivity is expressed as the reciprocal of the logarithm of the exposure amount required to obtain an optical density of fog value + 0.1, or in Table 3, the sensitivity of sample 13 is set as 100, and the others are expressed relatively. . The results obtained are shown in Table 3.

Processing liquid (developer for black and white photographic materials) l-Funito-3-pyrazolidone 1.5g
Hydroquinone 30g 5-nitroindazole 0.25g Potassium bromide anhydrous sodium sulfite Potassium hydroxide Boric acid Glutaraldehyde (25%) Add water to bring the total amount to IQ.

g 5g 0g 0g g As is clear from Table 3 above, Samples 14 to 17 using the compounds of the present invention are found to be more stable against heat and γ-rays than Sample 13 using a comparative compound.

Example 4 A monodisperse silver chlorobromide cubic grain emulsion (average grain size 0.35 μm) with a silver chloride content of 99 mol % contains 4 x 10-' moles of sodium thiosulfate per mole of silver halide and 2
X10-' moles of a gold compound and IX10-4 moles of the following red-sensitive sensitizing dye were added, and the mixture was heated and aged at 60°C for 60 minutes. At the end of ripening, l-phenyl-5-mercaptotetrazole was added as a stabilizer. Furthermore, an appropriate amount of the following yellow coupler (Y-1) and 2゜5-di-
t-Octylhydroquinone, dioctyl phthalate and the hardener described below were added. The various emulsions thus prepared were coated on polyethylene resin-treated paper supports and dried to obtain Samples 18 to 23.

These samples were exposed to wedge light using the usual method, and then processed according to the color development process described below, and then their photographic properties were comparatively evaluated.
;.

The results are shown in Table 4. Incidentally, the sensitivity was expressed in relative sensitivity as in Example 1°2.3.

(Red-sensitive sensitizing dye) (Processing process) Color development bleaching fixing temperature 34.7±0.3°C 34.7±0.5°C Time 45 seconds Stabilization 50 seconds 30-34°C 90 seconds drying 60 ~80℃ 60
Seconds (color developer) Pure water 800m (i Triethanolamine 8gN, N-
'; Ethylhydroxylamine 5g Potassium chloride 2g N-ethyl-N-β
-Methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 5
g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Potassium sulfite 0.2g Optical brightener (4,4
'-diaminostilbendisulfonic acid derivative)
Add 1g of pure water to bring the total volume to 14, and adjust the pH to 10.
Adjust to 2.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Denmonium thiosulfate (70% solution ff) 100mQ Ammonium sulfite (40% solution) 27.5ml 12 Adjust to pH 5.7 with potassium carbonate or glacial acetic acid Adjust and add water to bring the total volume to 10.

(Stabilizing solution) 5-chloro-2-methyl-4-inthiazolin 3-one Igl-hydroxyethylidene-1,1 diphosphonic acid 2g Water was added to make lα, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide.
Adjust to 0.

It can be seen that compared to Sample No. 18.19, it has less blurring, is highly sensitive, and is stable against heat.

Claims (2)

[Claims] (1) In a silver halide photographic light-sensitive material having a photographic constituent layer on a support, at least one of the photographic constituent layers is a silver halide emulsion layer, and at least one of the photographic constituent layers includes the following general A silver halide photographic material containing at least one of the sulfur-containing organic gold compounds represented by formulas [I] and [II]. (2) In the method for producing a silver halide photographic material,
The silver halide emulsion contained in at least one layer of the silver halide photographic light-sensitive material is chemically ripened in the presence of a sulfur-containing organic gold compound represented by the general formulas [I] and [II]. A method for producing a silver chemical photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, V and W are hydrogen atoms or substitutable groups (V and W
may be linked to form a ring), R is a hydrogen atom or a substitutable group, X^■ is an ion that cancels the intramolecular charge,
Y represents a hydrogen atom or a substitutable group, l represents an integer of 1 to 3, and m represents 2 or 3. However, ml is an integer of 0 to 2, and n represents the number of ions necessary to cancel the intramolecular charge. ]