JPH0470650A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To prevent an increase in fogging with lapse of time and the degradation in graininess by subjecting specific silver halide particles to gold sensitization in a chemical maturation stage in the presence of at least one of specific org. gold compds. CONSTITUTION:The silver halide particles in which >= 50 number % of the photosensitive silver halide particles incorporated therein contain >= 60 % silver bromide and which contain at least the silver bromide are subjected to the gold sensitization in the chemical maturation stage in the presence of at least one of the org. gold compds. expressed by formulas I and II. In the formulas I, II, R1 to R3 respectively denote a hydrogen atom or a group which can be substd.; Y denotes an oxygen atom, sulfur atom, selenium atom, tellurium atom or substd. or unsubsted. methylene group. X<-> denotes the ion which offsets and intramolecular charge. The increase in the fogging with lapse of time and the degradaion in the graininess are prevented in this way.

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.

[Prior art]

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, the amount of silver coating, and the weight ratio of the two contained in a photosensitive material per unit area to within a specific amount, and its realization. As a specific measure, a technique for removing gold (free gold)/or gold compounds that does not exist within or on the surface of silver halide grains is disclosed in JP-A-1-96642 and JP-A-1-96642.
It is disclosed in No. 96651, 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 these are not sufficient techniques to address the problem at hand. There is. Furthermore, it is considered that the technique 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 allerade (chloroauric acid), potassium chloroaurate, potassium auriothiocyanate, auric trichloride, etc. are currently generally used as suitable gold sensitizers. However, these total acid salts have the disadvantage that gold is easily liberated, and a part of the liberated gold forms a stronger complex with gelatin and remains in the 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, 50% by number of the photosensitive silver halide grains contained
The above are silver halide grains containing 60 mol% or more of silver bromide, and at least the silver halide grains containing silver bromide are organic gold compounds represented by A silver halide photographic emulsion that has been gold sensitized by a chemical ripening step in the presence of at least one.

Saburatsu (1) General formula (II) In the formula, R, , R, and R1 each represent a hydrogen atom or a substitutable group, and Y is an oxygen atom, a sulfur atom, a selenium atom,
Represents a tellurium atom or a substituted or unsubstituted methylene group.

Xo represents an ion that cancels out intramolecular charges.

In addition, R1°R in the above - killing CI) and [nl, ,
Substitutable groups represented by R and Y include hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, acylamino groups, alkylamino groups, ureido groups, amide groups, acyl groups, and carboxyl groups. represents.

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, l-
Examples include butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl group, and sulfoalkyl group.

Examples of the aralkyl group include benzyl group and phenethyl group; examples of the alkenyl group include allyl group and 2-butenyl group; examples of the aryl group include 7-enyl group and naphthyl group; these aryl groups can be substituted. may be substituted with a group.

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

Examples of the acyl 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.

Ions that cancel out the intramolecular charge represented by Xo are:
Examples include halogen ions (eg, Cl2e, Br'' ions), verchlorate, tosylate, hydroxide ions, and the like.

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

(I-1) (I-5) (d(II-1) (I-3) (II-2) CI-4) (■ (II-4) The compound of the present invention can be synthesized by a known method. For example, J, lnorg, nucl, Chem, Vol.
, 38.7-11 (1976), Transit
ion Met, Chem,, Vol, 2.224~
227 (1977) and JP-A-1-147537.

The gold compound of the present invention is preferably dissolved in water or a water-miscible solvent such as methanol, ethanol, or fluorinated alcohol, alone or in a mixed solvent, and added 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, the ripening conditions, etc., but it is usually I x 1 per mole of silver halide.
Preferably it is from 0-' mol to 1 x 10-' mol. More preferably I x 10-' mol to lx io
-”It is a mole.

Other chemical sensitizers can also be used in combination during 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, No. 2,278゜947, No. 3,50
No. 1,313, No. 3,656,955, West German Patent No. 1,422.869, Japanese Patent Publication No. 49-20533, Japanese Patent Publication 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-50-71320, etc., U.S. Pat.
No. 518,698, No. 2,521,925, No. 2,5
No. 21,926, No. 2,419,973, No. 2,69
Nos. 4,637 and 2,983,610, reducing substances such as amines and tin salts, U.S. Pat.
, No. 448,060, No. 2,566.245, No. 2,
Examples include salts of noble metals such as platinum, palladium, iridium, and rhodium, which are described in No. 566.263 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,
It can be used as a 7-tetrazaindene, guanosine, p-toluenesulfinic agent).

Specific examples include U.S. Patent No. 2,131.038;
411.

No. 914, No. 3,554,757, JP-A-58-12
No. 6526 and Duffin, "Photographic Emulsion Chemistry", published by 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 includes silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, etc.
A silver halide emulsion containing silver bromide of mol % or more can be used.

These silver halide emulsions are P.
．． Glafkides), Chimie et Physiic Photographic (Chimie et Physi
Que Photo.

graphique) (published by Paul Monte 1)
967); G.F.Dofin
f in), 7 Photographic Emulsion Chemistry
on Chemistry) (The Focal Pr.
ESS Published 196 Year 966 El Jerikman (V
, L., Zelikman) et al., Making and Coating 7 Autographic Emulsions (
Making and Coating PhoLgr
aphic Emulsion) (The Focal
It can be prepared using the method described in Press, 1969, 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 any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

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 in which pAg in the liquid phase in which /% silver halide is produced is kept constant, that is, 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 be one with a face or a (7) one-sided shape.

Further, the structure of the silver halide crystal may be a structure having a substantially uniform composition, a core/shell type double structure, 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 (shell 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.

The 7% silver halide crystal grains contained in the silver halide emulsion of the present invention may have different compositions of silver halide bonded to the parent silver halide crystal by epitaxial bonding, or , for example, may be bonded with a compound other than silver halide, such as silver thiocyanate or lead oxide. In addition, during the process of silver halide grain formation or physical ripening, chalcogen 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 A salt or an iron complex salt may also be present.

Also, Special Publication No. 58-1410, “Journal on Photographic Science” by Moyser et al., Volume 25 (
It is also possible to carry out reduction sensitization inside the silver norogenide crystal, as described in 1977), pp. 19-27.

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

The silver halide emulsions of this invention may be spectrally sensitized with methine dyes and others. Dyes that can be used include cyanine dyes, merocyanine dyes, 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.

For these dyes, any of the nuclei commonly used for cyanine dyes can be applied as a basic heterocyclic nucleus. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: namely, Indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a 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 containing a ketomethylene structure.
-Dione nuclei, thiazolidine-2,4-dione nuclei, rhodanine nuclei, thiobarbital acid radicals, and other 5- to 6-membered heterocyclic nuclei can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929,080;
U.S. Patent Nos. 2,231,658 and 2,493,748
No. 2,503゜776, No. 2,519,001, No. 2,912,329, No. 3,655゜394,
These are described in Japanese Patent No. 3,656.959, Japanese Patent No. 3,672,897, Japanese Patent No. 3,694°217, British Patent No. 1,242,588, Japanese Patent Publication No. 14030/1973, and the like.

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, No. 2,977.229, No. 3,39
No. 7,060, No. 3,522,052, No. 3,527
, No. 641, No. 3,617,293, No. 3,628,
No. 964, No. 3,666.480, No. 3,679,4
No. 28, No. 3,703,377, No. 3,769.30
No. 1, No. 3,814.609, No. 3,837,862
No., British Patent No. 1,344゜281, Special Publication No. 1973-49
It is described in issue 36 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 a nitrogen-containing heterocyclic group (eg, U.S. Pat. Nos. 2-933, 390 and 3,635).
721), 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. 3,61
No. 5,641, No. 3,617,295, No. 3,635
．． The combinations described in No. 721 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, but if it is added before the start of chemical sensitization, Good results are often obtained.

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, 1,000-onythyl compounds, thiomorpholines, and It may also contain class ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

For example, US special edition No. 2,400,532, US special edition No. 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 (Ar+t
ifoggan) and stabilizers
may contain. As a compound, rAnt in Product Licensing Index, Vol. 92, p. 107
Those described in the section of 100 Oggantsand 5LabilizersJ 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)
Examples include compounds described in

Additives Chemical sensitizers Sensitizing dye development accelerators Antifoggants Stabilizing agents Color stain inhibitors Image stabilizers Ultraviolet absorbers Fluor dye Brighteners Hardening agents Coating aids Surfactants Plasticizers Agent Static Inhibitor Matt Agent Binder RD-17643 Page Classification 23 I [I 23 rV 29 1!] 24 Vl 25 ■ 25 ■ 25-26 ■ // 4 V 6 X 26-27 n 26-27X1 27 11 [ ■ x ■ ■ RD-18716 Page Classification 648- Upper right 648 Right- Upper right 648- Upper right 649- Lower right // Left-Right 649 Right to 650 Left 651 Right 650 Right 650 Right 650 Right 651 Right Photosensitive materials according to the present invention The emulsion layer contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-)12-diamine derivative, aminophenol derivative, etc.) during color development processing. Couplers may also be used.

The dye-forming couplers are usually selected for each emulsion layer so that a dye is formed that absorbs light in the light-sensitive spectrum of the 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. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. , 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 the 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 group is separated by the coupling reaction. 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). Furthermore, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination depending on the purpose. Colorless couplers (also referred to as competitive couplers) that undergo a coupling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes can be used in combination 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. 3,725゜072, No. 3,8
91,445, West German Patent No. 1,547.868, West German Application No. 2,219.917, West German Patent Application No. 2,261.361
No. 2゜414.006, British Patent No. 425.0
No. 20, Special Publication No. 51-10783, Japanese Patent Publication No. 47-26
No. 133, No. 48-73147, No. 50-6341, 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 acylacetonitrile couplers, indacylon couplers, etc. can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat.
3゜062.653, 3,127.269, 3,311,476, 3゜419.391, 3
, 519,429, 3,558,319, 3゜582.322, 3,615.506, 3,8
No. 34,908, No. 3°891.445, West German Patent 1
, No. 810,464, West German Patent Application (OLS) 2,40
No. 8,665, No. 2,417.945, No. 2,418
．． No. 959, No. 2,424,467, Special Publication No. 1976-6
No. 031, JP-A-49-74027, JP-A No. 49-740
No. 28, No. 49-129538, No. 50-60233
No. 50-159336, No. 51-20826,
No. 51-26541, No. 52-42121, No. 52
No.-58922, No. 53-55122, Patent Application No. 1983-
Examples include those described in No. 110943 and the like.

As the cyan dye-forming coupler, known phenolic or 7-tole couplers can be used. For example, phenolic couplers substituted with an alkyl group, acylamino group, or ureido group, 7-toll couplers formed from a 5-aminonaphthol skeleton, 2-equivalent 7-toll couplers with an oxygen atom introduced as a leaving group, etc. is represented.

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. Examples of the support in this case include cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass, paper, metal, polyolefin,
For example, paper coated with polyethylene, polypropylene, etc. 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 for photographic processing is usually 18°C
~50°C, but even at temperatures below 18°C 50°
Processing is possible even at temperatures of C or higher.

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 in photosensitive materials for black and white photography such as ray photography, squirrel photography, micro photography, general photography, and black and white photographic paper.

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. 4,129,446, No. 4,186.016, British Patent No. 1,560°965, US 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-
No. 177552, British Patent No. 2,137.372, Japanese Patent Application Publication 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. 59-160135.

〔Example〕

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

A monodisperse core-shell type silver iodobromide emulsion (
Octahedral normal crystal, cubic equivalent grain size 1. A grain size variation coefficient of θμm1 of 16%, average silver iodide content of 9.5 mol%, and internal height deformation was prepared.

The emulsion was then divided into equal parts, each containing 14 spectral sensitizing dyes (D-1, D-2°D-3) per mole of silver halide.
0mg, ammonium thiocyanate 3.2X 10-
mol, 3-OX 10-' mol of sodium thiosulfate, and 8.0 mol of gold compound as shown in the table below. 10-" mol of OX was added and each was optimally sensitized (sulfur + gold) at 55°C. After that, 4-hydroxy-6-
850 methyl-1,3,3a,7-tetrazaindene
mg was added.

spectral sensitizing dye A゛　・I-U　.

1-(2,4,6-trichlorophenyl)-3 as a magenta coupler per mole of silver halide.
-[3,-(2,4-di-t-amylphenoxyacetamide)penzamide]-5-pyrazolone 80g1
As a colored magenta coupler, 1-(2,4,6-
Triclophenyl)-4-(1-su7tylazo)-3-
Weighed 2.5 g each of (2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone, followed by 120 g of tricresyl phosphate.

240 mg of ethyl acetate was mixed and dissolved by heating, and then a coupler solution emulsified and dispersed in a solution of 5 g of sodium triisocrovirnaphthalene sulfonate and 550 m of a 7.5% gelatin aqueous solution (2) was added to each of the above 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 coated silver amount of 2.0 g/m''. Samples 1 to 6 were obtained by coating on a triacetate support and drying.

A portion of the sample prepared as described above was allowed to stand for one day.

The other part was placed in an atmosphere with a temperature of 55℃ and a relative humidity of 20%.
It was stored for several days and used as a forced deterioration sample. Also, the other part is “Go”
It was irradiated with γ-rays from LOOO+oR and used as a sample for estimating the degree of influence of natural radiation. These various samples were subjected to wedge exposure in a conventional manner, color developed according to the following color processing steps, and their photographic properties were comparatively evaluated.

The results are shown in Table 1. Note that the sensitivity in the table is expressed as relative sensitivity.

Processing process Processing temperature 38°C Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Washing 3 minutes 15 seconds Fixation 6 minutes 3
Wash with water for 0 seconds 3
Stabilization for 1 minute and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid 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 (monohydrate) 2.5g potassium hydroxide
Add 1.0g of water to make it 112, and use sodium hydroxide to set the sensitivity of comparative sample l left at room temperature to 100.
Adjust the pH to 10.6.

(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 112
and adjust the pn to 6.0 using aqueous ammonia.

(Constant tank solution) Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make H2, and adjust to pH 6.0 using acetic acid.

(Stabilizing liquid) Formalin (37% aqueous solution) 1.5m
(2Konidax (Konica C stock) IL)
Add 7.5 mQ water to make lf2.

As is clear from Table 1 above, samples 3 to 6 using the compounds of the present invention were compared to samples 1.2 using the comparative compounds.
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 jet method as in Example 1. The average shape modification content of the emulsion grains is 10
．． 0 mol% (internal height deformation), cubic equivalent particle size is 1.2
The μm1 particle size variation coefficient was 24%, and the 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, 1-ethyl-3-(2-thiazolyl)thio atom was used instead of sodium thiosulfate. The results are shown in Table 2, and the comparative compounds are the same as in Example 1. Also, assuming the sensitivity of sample 7 to be 100,
Others are 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 and 8 using comparative compounds.

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

The emulsion was then divided into equal parts, each containing 1 part of silver chloride.
4.4 x 10-' mol of sodium thiosulfate, 1.2 x 10-3 mol of ammonium thiocyanate,
Add 1.2X 10-'mol of gold compounds shown in Table 3,
Each was optimally sensitized (sulfur + gold) at 5°O;
.

After chemical ripening, each emulsion contains 4-hydroxy-6 as a stabilizer.
-Methyl-1,3,3a,7-tetrazaindene, saponin as a coating aid, and 2,4-dichloro-6-hydroxy-S-triazine as a hardening agent were added in appropriate amounts.

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 6
γ-rays from 0Co 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, washed with water, dried, and then photographed. (Sensitivity and fog) were measured.

Note that 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, but 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) ■-Phenyl-3-pyrazolidone 15g Hydroquinone 30g 5-nitroindazole 0.25g Potassium bromide 5g Anhydrous sodium sulfite 55g Potassium hydroxide
30g boric acid
10g glutaraldehyde (25%) Add 5g water to IQ
shall be.

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

Claims (1)

[Scope of Claims] Silver halide grains in which 50% by number or more of the photosensitive silver halide grains contained are silver halide grains containing 60 mol% or more of silver bromide, and which contain at least the silver bromide. 1. A silver halide photographic emulsion characterized in that it has been subjected to gold sensitization in a chemical ripening step in the presence of at least one organic gold compound represented by the following general formulas [I] and [II]. 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, R_1, R_2 and R_3 each represent a hydrogen atom or a substitutable group. and Y represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or a substituted or unsubstituted methylene group. X^■ represents an ion that cancels the intramolecular charge. ]