JPH049942A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To enhance the sensitivity of the emulsion by forming catalyst nuclei on silver halide crystals and forming chemical sensitizing nuclei in the presence of a prescribed compd. CONSTITUTION:This emulsion is formed by forming the nuclei (catalyst nuclei) which exert a catalytic effect on the silver sulfide forming reaction on the surface of the silver halide crystals and accelerate the reaction thereof on the above-mentioned crystal surface and forming the chemical sensitizing nuclei consisting of silver sulfide or gold sulfide or the mixture composed thereof on these crystals in the presence of the compd. (A) having adsorptivity to the crystals. A sulfur sensitizer and gold sensitizer are usable for forming the catalyst nuclei and the formation of the chemical sensitizing nuclei by using thiosulfate, etc., is possible as well.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic emulsion, particularly a highly sensitive silver halide photographic emulsion.

[Background of the Invention] In recent years, demands for silver halide photographic emulsions for photography have become more and more intense, and demands for photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density, and sufficiently high optical density have become increasingly high. standards are being demanded. 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.

The most legitimate way to achieve high sensitivity is to reduce inefficiency in the photosensing process of silver halide crystals and improve quantum efficiency. Conventionally, as a means to improve this quantum efficiency, it has been possible to form and impart chemical sensitizing nuclei consisting of silver sulfide, gold sulfide, or a mixture thereof, which function as photosensitive centers that capture photoelectrons, on the surface or inside of silver halide crystals. This is generally known as sulfur sensitization or gold-sulfur sensitization.

However, when conventional chemical sensitization methods are used to form chemical sensitizing nuclei with high electron capture efficiency, a large number of chemical sensitizing nuclei are formed, and each chemical sensitizing nucleus generates photoelectrons during the photosensitization process. It is known that competition for capture leads to a decrease in latent image formation efficiency, that is, a decrease in sensitivity.

As a means to improve these drawbacks of conventional methods, a technique has been proposed in which a so-called chemical sensitization control agent or chemical sensitization modifier is present in the chemical sensitization process to control the chemical sensitization nucleation process. ing. For example, JP-A-58-126526, JP-A-1201651, US Pat. No. 2,131,038, US Pat. No. 3,411.914,
No. 3,554,757 and "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (1966), 138-
It is described on page 143. Further, as other improvement measures, various methods for selectively growing chemical sensitization at singular points on silver halide crystals are disclosed in JP-A-61-93447.

However, as a result of our studies, we found that the recent demand for higher sensitivity cannot be fully achieved with these improvement measures.

[Purpose of the invention]

Accordingly, the first object of the present invention is to provide a silver halide photographic emulsion that is highly sensitive by improving the chemical sensitization nucleation process. The second object is to provide a method for producing a highly sensitive silver halide photographic emulsion.

C Structure of the Invention] An object of the present invention is to provide a nucleus (catalytic nucleus) capable of exerting a catalytic effect on the silver sulfide formation reaction on the surface of the silver halide crystal and promoting the reaction on the surface of the silver halide crystal. This was achieved using a silver halide photographic emulsion in which chemically sensitized nuclei consisting of silver sulfide, gold sulfide, or a mixture thereof were formed in the coexistence of a compound adsorbed to silver halide crystals.

The present invention will be explained in detail below.

The nucleus capable of exerting a catalytic action on the silver sulfide formation reaction I and promoting the reaction (catalytic nucleus) is defined in the above-mentioned Japanese Patent Application Laid-open No. 61-9
This is different from the unique location on a silver halide crystal defined in No. 3447. That is, the catalyst nucleus in the present invention is a singular point consisting of an element or a combination of elements different from the elemental composition of silver halide. Specifically, Au, Pt
, Ir, noble metal elements such as Pd or/and S,
It is a singular point made of elements such as Se and Te or compounds thereof, such as silver sulfide, gold sulfide, silver selenide, and gold selenide. Note that the present invention is not limited to these elements and compounds.

Whether or not these singular points function as catalyst nuclei to promote the silver sulfide formation reaction can be determined by measuring the rate of the silver sulfide formation reaction caused by the sulfur sensitizer. The reaction rate of the silver sulfide formation reaction can be measured by various methods, including tracing the reaction using a sulfur sensitizer labeled with a radioactive element, spectroscopically measuring the amount of silver sulfide produced, Methods for measuring changes in the concentration of proton ions released by the reaction of a sulfur sensitizer are known in the art. By H, Takiguchi: J, I, respectively.
g+agingSci, vol. 32, p. 20 (198
g), by E. Molsar: Ber, d.

Bunsenges, Phys, Chem, vol. 72, p. 467 (1968), D. J. Ca5h: J.
Photogr, Sci, + vol. 20, p. 107 (19
72) etc. may be helpful.

The step of forming catalyst nuclei is preferably performed before the step of forming silver sulfide using a sulfur sensitizer. Furthermore, as the element or compound used to form the catalyst nucleus, elemental sulfur, the following sulfur sensitizers, gold sensitizers, selenium sensitizers, etc. can be used for this purpose.

The appropriate amount (W molecules or number of molecules) for this purpose varies depending on the conditions of various factors such as the silver halide crystal and the chemical sensitization process.
/3 or less is preferable.

The sulfur sensitizer used to generate silver sulfide in the present invention can be selected from water-soluble sulfide salts, thiosulfates, thioureas, mercapto compounds, rhodanines, and the like.

Specific examples of these are U.S. Pat. No. 1.574,944, U.S. Pat.
No. 01313, No. 3,656.955, West German Patent No. 1,422,869, Japanese Patent Publication No. 49-20533, Japanese Patent Publication No. 5g-28568, etc.

Among these, thiosulfates, thioureas, and rhodanines are preferred, and thiosulfates are particularly preferred. The amount of the sulfur sensitizer to be used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc. Usually, I; sl x 10-
'~1X10-' moles are preferred. More preferably, it is l x 10-5 to l x 10-' mol. It is preferable to add the sulfur sensitizer slowly over time. Further, in order to cause the sulfur sensitizer to react slowly, the reaction temperature is preferably lower, and is preferably in the range of 40 to 60°C. Further, the silver ion concentration of the reaction system (silver halide emulsion) is preferably low, and pAg (absolute value of the logarithm of the reciprocal of the silver ion concentration) is preferably 8.0 to 11.0.

Examples of compounds adsorbable to silver halide crystals used in the present invention include stabilizers, antifoggants, and spectral sensitizing dyes.

Stabilizers and antifoggants include, for example, azaindenes, azoles, such as benzothiazolium salts, nitrointasoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, and mercaptobenzimidazoles. mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinthion, Further examples include benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, and ascorbic acid derivatives. Among these, azaindenes are preferred.

Typical specific examples are listed below, but the invention is not limited to these.

A-12,4-dihydroxy-6-methyl-1,3a,
7-triazaindene A-22,5-dimethyl-7-hydroxy-1,4,7
a-triazaindene A-35-amino-7-hydroxy-2-methyl 1.4
．． 7a-) Riazaindene A-44-hydroxy-6-methyl-1,3,3a,7
-Chitrazaindene 8-54-Hydroxy-1,3,3a,7-Chitrazaindene A-14 4-hydroxy-6-7 Enyl 1.3.3a,7-
Chitrazaindene 4-methyl-6-hydroquine-1.3.3a,7-chitrazaindene 2,6-dimethyl-4-hydroxy-1,3,
3a, 7-chitrazaindene 4-hydroxy-5-ethyl-6-methyl 1,3,3a
,7-chitrazaindene 2,6-dimethyl-4-hydroxy-5-ethyl 1,3
．． 3a,7-tetrazaindene 4-hydroxy-5,6-dimethyl-1.3.3a,7
-thitrazaindene 2,5,6-)trimethyl-4-hydroxy-1,3.
3a.

7-Chitrazaindene 2-tin-4-hydroxy-6-phinyl 1.3.

3a,7-thitrazaindene 4-hydroxy-6-methyl-1.2.3a, 7-thitrazaindene 4-hydroxy-6-ethyl-1.2.3a, thitrazaindene A-164-hydroxy-6-7enyl-1 .2.3a
, 7-chitrazaindene A-174-hydroxy-1.2.3a. 7-chitrazaindene A-184-methyl-6-hydroxy-1.2,3a,
7-Chitrazaindene A-197-hydroxy-5-methyl-1.2.3.4
．． 6-pentazaindene A-205-hydroxy-7-methyl-1.2,3,4
．． 6-Pentazaindene A-21. 5.7-Sihydrox7-1.2.3,4
．． 6-Pentazaindene A-227-hydroxy-5-methyl-2-7enyl-1,2.

3,4.6-pentazaindene A-235-dimethylamino-7-hydroxy-2-phenyl-1.2,3,4.6-pentazaindene As the sensitizing dye preferably used in the present invention, 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.

Any of the nuclei commonly used for cyanine dyes can be applied to these dyes as basic heterocyclic nuclei. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, virol 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 melonanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2,4 nucleus having a ketomethylene structure.
-Dione nuclei, thiazolidine-2,4-dione nuclei, rhodanine nuclei, thiobarbital acid roots, and other 5- to 6-membered heterologous 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,
This invention is 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. 1.344281, Special Publication No. 43-493
It is stated in issue 6 etc.

Typical specific examples of sensitizing dyes used in the present invention are shown below, but the compounds that can be used in the present invention are not limited to these.

■ CH.

CH.

C, H.

CI(,CH,CHSO,e C.O.

C,H.

C,H.

(CHJ+SO+e CH3 shiHl (shiH2), SU, H and N(CzH,)s ((Jx
], SO, - 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, aminotilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. Nos. 2,933,390 and 3,6
35.721), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743.510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615゜613, No. 3
, 615.641, 3,617.295, 3,
The combinations described in No. 635.721 are particularly useful.

In the chemical sensitization nucleation process of the present invention, the compound capable of adsorbing silver halide and coexisting as a control agent may be one type or a combination of a plurality of types of compounds. In the case of a silver halide emulsion that requires spectral sensitization, it is preferable to use a spectral sensitizing dye in combination as a control agent for the chemical sensitization process. In this case, preferable results can often be obtained by increasing the coverage of the surface of the silver halide crystal by using compounds such as the above-mentioned stabilizers and antifoggants.

The coverage of the silver halide crystal surface by the adsorptive compound is preferably 50% or more, more preferably 70% or more.

In the present invention, as the gold sensitizer that can be used in combination, the oxidation number of gold may be +1 or +3, and various gold compounds can be used. Representative examples include chlorauric acid salts, potassium chloroaurate, auric trichloride, potassium auric thionanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like.

The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is approximately 10-7 to 10-1 per mole of silver halide.
A molar range is preferred. Incidentally, it is preferable to add it after the silver sulfide formation process is completed.

In the present invention, other chemical sensitizers that can be used in combination include:
For example, aliphatic inselenocyanates such as allyl isoselenocyanate, selenium ureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenophosphates, diethylselenide, selenium-enhancing selenium such as diethylselenide, diethylselenide, etc. Sensitizing agents can be used, specific examples of which are described in US Pat. No. 1,574.
No. 944, No. 1,602,592, No. 1,623.4
It is described in No. 99, etc. Also, U.S. Patent No. 2,487,
No. 850, No. 2,518.698, No. 2,521,9
No. 25, No. 2,521.926, No. 2,419.97
No. 3, No. 2,694,637, No. 2,983,610
Reducing substances such as amines and tin salts described in U.S. Patent Nos. 2,448,060 and 2,566.
Examples include salts of noble metals such as platinum, palladium, iridium, and rhodium, which are described in No. 245, No. 2,566.263, 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.

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 0 Photograph (''/ri)
ePhotographiqueXPaul Mont
e1 company flJ] 957) r'; -- Written by F. Duffin (G, FDuff in), Photographic Emulsion Chemistry
Emulsion Chemisty
al Press Published 196 Year 966 Co-authored by V, L, Zel ikman and others, Making and Coating Photographic 0 Emulsion (Makingand CoatingPh
otographic E [IIulsion) (Th
e Focal Press, 196, 964). That is, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as the method of reacting the soluble silver salt and the soluble halogen salt, a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used.

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 II) Ag 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 emulsion of the present invention may be narrow or wide.
It may be a regular shape such as an octahedron or a tetradecahedron, or may have a variable U-like crystal shape such as a spherical shape, a crystal shape having twin planes, or a composite shape thereof. Further, the structure of the silver decagenide 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, the interior (core part)
It is preferable that the shell portion and the surface layer portion (shell portion) have different halogen compositions.

The present invention can also be applied to the sensitization of tabular silver halide grain emulsions. Here, the term “tabular silver halide grain” refers to its diameter/
The thickness ratio is 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 epitaxial 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,
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 salts or iron complex salts, etc. may be coexisting.

Also, Special Publication No. 58-1410, “Journal of 7 Autograph Science” by Moyser et al., Volume 25 (
It is also possible to carry out reduction sensitization inside the silver halide crystal as described in 1977), pp. 19-27.

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, thiomol-7-olins, and quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or accelerating development. It may also contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

For example, U.S. Patent Nos. 2,400,532 and 2,423,
No. 549, No. 2,716.062, No. 3,617.2
Those described in No. 80, No. 3,772,021, No. 3808003, etc. can be used.

The silver halide emulsion of the present invention can contain antifoggants and stabilizers even after the chemical sensitization step.
tabilizer). As a compound,
rAntifogantsand 5 in Product Licensing Index, Volume 92, p 107
Those described in the section of tabilizers 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).

Below are margin additives, chemical sensitizers, sensitizing dye development accelerators, antifoggants, stabilizers, color stain inhibitors, image stabilizers, ultraviolet absorbers, filters, dye brighteners, hardening agents, coating aids, surfactants, plasticizers, and slippers. Anti-Static Agent Mantle Agent Binder RD-17643 Page Classification 23 1 [1 23TV 29 llI 24 Vl // 25 ■ 25 ■ 25-26 ■ 4 V 6 X 26-2711 26-27 I[ 7m ■ VI ■ RD - 18716 pages Classification 648 - Upper right 648 Right - Upper right 648 - Upper right 649 - Lower right left - Right 649 Right - 650 Left 651 Right 650 Right 650 Right 650 Right 651 Right The emulsion layer of the light-sensitive material according to the present invention has color development. In the processing, a dye-forming coupler that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (eg, p-] dinylene diamine derivative, amine phenol derivative, etc.) may be used.

The dye-forming couplers are typically selected for each emulsion layer to form a dye 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 combinations.

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). 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 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 Patent Application No. 2,219,917, West German Patent No. 2,261,361
No. 2゜414.006, British Patent No. 1,425,0
No. 20, Special Publication No. 51-10783, Japanese Patent Publication No. 47-26
No. 133, No. 48-73147, No. 5゜6341,
No. 50-87650, No. 50-123342, No. 5
No. 0-130442, No. 51-21827, No. 51-
No. 102636, No. 52-82424, No. 52-11
No. 5219, 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, 3419.391, 3,
No. 519,429, No. 3,558,319, No. 3゜5
No. 82.322, No. 3,615,506, No. 3,83
No. 4,908, No. 3°891.445, West German Patent No. 1,
No. 810,464, West German Patent Application (OLS) 2,408
, No. 665, No. 2,417,945, No. 2,418,
No. 959, No. 2,424,467, Special Publication No. 1977-1960
No. 31, JP-A-49-74027, JP-A No. 49-7402
No. 8, No. 49-129538, No. 5060233,
No. 50-159336, No. 51-20826, No. 5
No. 126541, No. 52-42121, No. 52-58
No. 922, No. 53-55122, patent application No. 55-110
Examples include those described in No. 943 and the like.

As the dye-forming coupler, known phenolic or naphthol couplers can be used. Typical examples include phenolic couplers substituted with an alkyl group, acylamino group, or ureido group, naphthol couplers formed from a 5-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, 19
No. 3, 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, 61-5
No. 0136, No. 61-99141, No. 61-1055
Examples include those described in No. 45.

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, undercoating treatment, and heptadation treatment. etc. are 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 photosensitive materials such as color reversal film, color photographic paper, color positive film, color reversal medium paper, direct positive, thermal development, silver die bridge, etc., as well as for X-ray photography, squirrel photography, micro photography, and general photography. It can be used in black-and-white photographic materials such as , black-and-white photographic paper, and the like.

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, 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.

In the following margins [Examples] 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 1.3 μm, a grain size variation distribution of 18%, an average silver iodide content of 7.6 mol%, and a high internal iodine type were prepared.

The emulsion was divided into equal parts, the sulfur compounds or gold compounds shown in Table 1 were added to each part, and the mixture was kept at 60°C for 1 hour to form catalyst nuclei. 4-hydroxy-6-methyl to 1.3.3a per mole of silver halide, respectively;
90 mg of 7-chitrazaindene was added.

After cooling to 50° C., sodium thiosulfate partially labeled with 3ss, which is a radioactive element, was added at 3.0% per mole of silver halide as a reagent for producing silver sulfide. Ox 1
The reaction rate was measured by tracing the radioactive element using 0-' mol.

As a comparative emulsion, an emulsion was prepared in which the same amount of the above azaindene compound was added without any special catalyst nucleus.

The method for measuring the reaction measure is described in the above-mentioned document, J, 1magin.
The method described in G Sci, Vol. 32, p. 20 (1988) was followed.

Table 1 S-■ Au -I The measurement results of the reaction rate of the silver sulfide production reaction using sulfur element chloroauric acid sodium thiosulfate are shown in Table 2.

As is clear from the results in Table 2, the rate of silver sulfide production in the emulsion to which catalyst nuclei were added before adding sodium thiosulfate was faster than in comparison.

Example 2 To the same emulsion (E m, -1 to 4) as in Example 1, the same amount of non-radioactive sodium thiosulfate was added instead of radioactive tonalium thiosulfate over 1 hour, and chemical ripening was performed. did.

After chemical ripening, each emulsion was further treated with 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene as a stabilizer, saponin as a coating aid, and 2,4-dichloro-6-hydroxy- as a hardener. An appropriate amount of s-triazine was added.

Each of the obtained emulsions was coated on a subbed polyester support and dried to obtain Samples 1 to 4.

These samples were exposed to light (1150 seconds) using a conventional sensitometric wedge, and then subjected to the following treatment for 3
After developing for 30 seconds at 5°C, fixing, washing with water, and drying, photographic properties (sensitivity and capri) were measured.

The results obtained are shown in Table 3.

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 1 is set as 100, and the others are expressed relatively. did.

Processing liquid (developer for black and white photographic materials) ■-Phenyl-3-pyrazolidone 1.5g
Hydroquinone 30g 5-nitroindazole 0.25g Potassium bromide 5g Anhydrous sodium sulfite 55g Potassium hydroxide
30g nitric acid
10g glutaraldehyde (25%) 5g
Add water to bring the total volume to 112.

As is clear from Table 3, Sample 2 using the emulsion of the present invention
, 3.4 is found to have higher sensitivity than sample 1.

Example 3 An emulsion consisting of tabular grains was prepared by the same double jet method as in Example 1. The average legality content of the emulsion grains is 9
．． 8 mol% (internal high iodine type), cubic equivalent particle size is 1.2
The μm1 particle size variation coefficient was 20%, and the diameter/thickness ratio was 4.3.

The emulsion was then divided into equal parts, one of which was designated Em5 and was designated as a comparison emulsion. In another method, the total complex of 5,5-dimethylrhodanine was added at 2.5X per mole of silver halide.
Example-
Em-6 was applied in the same manner as in Example 1.

Next, for E m -5, 170a+g of spectral sensitizing dyes (D-1, D-2, D-3) were added per mole of silver halide.

Optimal (sulfur-rich) sensitization was performed at 50°C by adding 4 x 10-' mol of ammonium thiocyanate, 3.7 x 10-' mol of sodium thiosulfate, and 1.0 x IO-' mol of chloroauric acid. .

Em-6 contains the same amounts of the same spectral sensitizing dyes (D-1 to D-3) and ammonium thionate as above, and 4-hydroquine-6.
-Methyl-1,3,3a,7-chitrazaindene 20ω
g was added. Next, add 3.7X 10 sodium thiosulfate
-' mol was added over 1 hour and subjected to optimal sensitization at 50°C.

Thereafter, 4-hydroxy-6-methyl 1.
3. 850 mg of 3&,7-chitrazaindene was added.

Spectral sensitizing dye (CHx)3sOsH'N(C2Hs)s (CH,)
, S□, e then 1-(2,4,6-trichlorophenyl)3-[3-(2,4-di-t-amylphenoquine acetamido)benz as magenta coupler per mole of silver halide. Amide 1-5-pyrazolone 80
g1 As a colored magenta coupler, 1-(2,4
,6-triclophenyl)-4-(1-naphthylazo)
Weighed 2.5 g of -3-(2-chloro-5octadecenylsuccinimidoanilino)-5-pyrazolone, mixed them with 120 g of tricresyl phosphate and 240 mg of ethyl acetate, and dissolved them by heating. A coupler solution emulsified and dispersed in a solution of 5 g of sodium triisopropylene 7talenesulfonate and 550 t12 of a 7.5% aqueous gelatin solution was added to each of the above emulsions.

Next, after uniformly adding an appropriate amount of sodium 2-hydroxy-4,6-dichlorotriazine as a hardening agent, each emulsion was coated with a coated silver coating of 2-0 g/m''. Samples 5 and 6 were obtained by coating on a triacetate support and drying.

Samples 5 and 6 were wedge-exposed in a conventional manner, developed in color according to the following color processing steps, and comparatively evaluated for photographic properties. The results are shown in Table 4.

Note that the sensitivity in the table is expressed as a relative sensitivity with the sensitivity of Comparative Sample 5 as 100.

Processing process (processing temperature 38°C) Processing time Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds fixed
Arrive 6 minutes 30 seconds Wash 3 minutes 15
Stabilization for 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 phosphorus sulfate anhydrous sodium sulfite hydroxylamine 1/2 sulfate anhydrous potassium carbonate sodium bromide nitrilotriacetic acid 4.75 g 4.25g 2.0g 37.5g 1.3g Water salt) 2.5g Potassium hydroxide Add 1.0g water and seal, adjust pH to 10 using sodium hydroxide,
Adjust to 6.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make 112, and adjust to pH 6.0 using aqueous ammonia. do.

3 Sodium salt (Fixer) Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to 11
2 and adjust the pH to 6.0 using acetic acid.

(Stabilizing liquid) Formalin (37% aqueous solution) 1.5 m (
1 Konida, Tsukusu (manufactured by Funica C Co., Ltd.) 7.5
Add +aQ water to make lI2.

Table 4 As is clear from Table 4, Sample 6 using the emulsion of the present invention has higher sensitivity than Comparative Sample 5.

Claims (1)

[Claims] A nucleus (catalyst nucleus) capable of acting catalytically on the silver sulfide formation reaction on the surface of the silver halide crystal and promoting the reaction is present on the surface of the silver halide crystal, and 1. A silver halide photographic emulsion characterized in that chemically sensitized nuclei made of silver sulfide, gold sulfide, or a mixture thereof are formed in the coexistence of an adsorbent compound.