JP2699033B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material. In particular, the present invention relates to a silver halide photographic material using a silver halide emulsion having improved fog and a change in sensitivity during storage.

[0002]

2. Description of the Related Art A silver halide emulsion used for a silver halide photographic light-sensitive material is usually subjected to chemical sensitization using various chemical substances in order to obtain desired sensitivity, gradation and the like. As typical methods, various methods of sensitization by sulfur sensitization, selenium sensitization, sensitization of noble metals such as gold, reduction sensitization, and a combination thereof are known. In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, as well as rapid processing that hastened development and the like.
Various improvements of the sensitization method have been made. Of the above sensitization methods, selenium sensitization is described in US Pat. No. 1,574.
No. 944, No. 1602592, No. 1623499
No. 3,297,446, No. 3,297,447, No. 332,0069, No. 3,408,196, No. 34
08197, 3434453, 34206
No. 70, 3591385, French Patent No. 2093
No. 038, No. 2093209, JP-B-52-344
Nos. 91, 52-34492, 53-295, 57-22090, JP-A-59-180536, 59-185330, 59-181337, and 5
Nos. 9-187338, 59-192241, 60
-150046, 60-151637, 61-
No. 246938, British Patent Nos. 255,846 and 86
1984 and H.S. E. FIG. HE Spencer
Authors, Journal of PhotographicScience, Volume 31,
158-169 (1983).

[0003]

However, selenium sensitization generally has a larger sensitizing effect than sulfur sensitization usually performed in the art, but tends to generate large fog and tend to be easily softened. There are many. Many of the above-mentioned known patents improve on these drawbacks, but they have only provided inadequate results, and there has been a keen need for fundamental improvements, especially for suppressing fogging. Also,
Particularly when sulfur sensitization and selenium sensitization are used together with gold sensitization, a remarkable increase in sensitivity can be obtained, but fog also increases.
Compared to gold-sulfur sensitization, gold-selenium sensitization has a particularly large fog increase and technology development to suppress fog generation, especially the development of a selenium sensitizer with little change in sensitivity during storage and less fog generation. It was strongly desired.

An object of the present invention is to provide a high-sensitivity silver halide photographic material having less fog.

[0005]

The object of the present invention is to provide a silver halide photographic material comprising a selenium-sensitized emulsion selenium-sensitized with at least one compound represented by the following general formula (I). Thus, the sensitizing effect of selenium sensitization, which was difficult with conventional techniques, can be fully utilized. General formula (I)

[0006]

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In the formula, R ₁ represents an aliphatic group, an aromatic group, a heterocyclic group, OR ₃ or NR ₄ R ₅ , R ₂ represents OR ₃ or NR ₄ R ₅ , R ₃ , R ₄ and R ₅ is a hydrogen atom,
Represents an aliphatic group or an aromatic group. Next, the general formula (I) will be described in detail. In the general formula (I), R ₁ , R
_The aliphatic group represented by ₃ , R ₄ and R ₅ preferably has 1 to 30 carbon atoms, and particularly has 1 to 20 carbon atoms, such as a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. It is. Here the branched ones may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Examples of the alkyl group, alkenyl group and alkynyl group include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group and cyclohexyl Group, allyl group,
2-butenyl, 3-pentenyl group, professional path Rugiru group,
And a 3-pentynyl group.

In the general formula (I), R ₁ , R ₃ , R ₄
And carbon aromatic group is preferably represented by R ₅ 6 to 3
0 and particularly a monocyclic or condensed aryl group having 1 to 20 carbon atoms, such as a phenyl group and a naphthyl group.

In the general formula (I), the heterocyclic group represented by R ₁ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Group. These may be monocyclic,
Further, a condensed ring may be formed with another aromatic ring or hetero ring. The heterocyclic group is preferably a 5- to 6-membered aromatic aromatic heterocyclic group, for example, a pyridyl group, imidazolyl group, quinolyl group, benzimidazolyl group, pyrimidyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group, thienyl Group, furyl group, benzothiazolyl group and the like. Further, the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group may be substituted. Examples of the substituent include the following.

A halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl, etc.) , an alkenyl group (e.g. allyl, 2-butenyl, 3-pentenyl group), alkynyl group (e.g. pro Pas Rugiru group,
3-pentynyl group, aralkyl group (eg, benzyl group, phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, 4-methylphenyl group), heterocyclic group (eg, pyridyl group, furyl group, imidazolyl group, piperidines <br/> lysyl group, morpholyl group, etc.), alkoxy groups (e.g. methoxy group, an ethoxy group, a butoxy group, etc.), an aryloxy group (e.g., phenoxy group, naphthoxy group, etc.), an amino group (e.g., unsubstituted amino group Dimethylamino group, ethylamino group, anilino group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.) ureido group (eg, unsubstituted ureido group, N-methylureido group, N
-Phenylureido group, etc.), urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), sulfonylamino group (eg, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (eg, sulfamoyl group, N-methyl) A sulfamoyl group, an N-phenylsulfamoyl group, etc.), a carbamoyl group (eg, carbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group, etc.), a sulfonyl group (eg, methylsulfonyl group, benzenesulfonyl group, etc.),
Sulfinyl group (eg, methylsulfinyl group, phenylsulfinyl group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), acyl group (eg, acetyl group, benzoyl group) Group, formyl group, pivaloyl group, etc.), acyloxy group (eg, acetoxy group, benzoyloxy group, etc.),
Phosphoric acid amide group (eg, N, N-diethylphosphoric acid amide group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), arylthio group (eg, phenylthio group, etc.), cyano group, sulfo group, carboxy group, hydroxy group , A phosphono group, a nitro group and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different. (R ₄ and R ₅ may be bonded to each other to form a ring, preferably a 5- to 6-membered ring, for example, pyrrolidine, piperidine, morpholine, and hyperazine). Specific examples of the compound are shown below, but the compound of the present invention is not limited thereto.

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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The compound represented by the general formula (I) can be generally synthesized by reacting various acid halides with sodium selenide or sodium hydrogen selenide, but can be synthesized according to the method described in the following literature. it can. Chemical Letters (Chem. Lett.), 401 (1972) Journal of the Chemical Society of Japan, No. 7, 1430 (1987) Journal of Synthetic Organic Chemistry, Vol. 43, No. 7, 660 (1985)

Heretofore, no specific examples using the compound of the general formula (I) as a selenium sensitizer have been reported. Therefore, it was extremely difficult to predict the sensitizing effect, fog, and other photographic effects of these compounds,
A remarkable effect was obtained by using the compound of the present invention. The amount of the selenium sensitizer used in the present invention depends on the selenium compound used, silver halide grains,
In general, it depends on the conditions of chemical ripening.
10 ^-8 to 10 ^-4 mol, preferably 10 ^-7 to 10 per mol
^Use about ^-5 moles. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pAg is 6 to 11,
The temperature is preferably 7 to 10, more preferably 7 to 9.5, and the temperature is 40 to 95 ° C, preferably 50 to 85 ° C.
° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium in combination. In particular, it is preferable to also perform gold sensitization agent include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and the like, per mol of silver halide, 10 ^{- About 7} to 10 ^-2 mol can be used.

In the present invention, it is preferable to further use a sulfur sensitizer in combination. Specific examples include known unstable sulfur compounds such as thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.) and rhodanines. About 10 ^-7 to 10 ^-2 mol can be used per 1 mol.

In the present invention, a reduction sensitizer can also be used in combination. Specifically, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, And the like.

In the present invention, selenium sensitization is preferably performed in the presence of a silver halide solvent. Specifically, thiocyanates (eg, potassium thiocyanate, etc.), thioether compounds (eg, US Pat.
No. 21215, No. 3271157, Japanese Patent Publication No. 58-30
No. 571, JP-A-60-136736 and the like, in particular, 3,6-dithia-1,8-octanediol and the like, tetrasubstituted thiourea compounds (for example, JP-B-59-1)
No. 1892, the compounds described in U.S. Pat. No. 4,221,863, especially tetramethylthiourea), and the thione compounds described in JP-B-60-11341, JP-B-63
No. 29727, mercapto compounds described in JP-A-60
And the selenoether compound described in U.S. Pat. No. 4,781,2013, the telluroether compound described in Japanese Patent Application No. 63-173474, sulfites and the like. In particular, among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used. The amount used is 10 ^-5 to 10 ^-2 per mol of silver halide.
About moles can be used.

The silver halide emulsion used in the present invention is:
Silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride are preferred. Silver halide grains used in the present invention,
Those having a regular crystal form such as cubic or octahedral, or irregular (irregu) such as spherical or plate-like
lar) crystal form or a compound form of these crystal forms. Although a mixture of particles of various crystal forms can be used, it is preferable to use a regular crystal form. The silver halide grains used in the present invention may have different phases in the inside and the surface layer, or may have a uniform phase. Also, grains whose latent image is mainly formed on the surface (eg, a negative emulsion) may be formed, and grains whose main image is mainly formed inside the grains (eg, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) It may be. Preferably, the particles are such that the latent image is mainly formed on the surface. The silver halide emulsion used in the present invention has a thickness of 0.5 μm or less, preferably 0.3 μm or less and a diameter of preferably 0.6 μm or more,
Particles with an average aspect ratio of 5 or more account for 50% of the total projected area
Either the average grain emulsion occupying the above or the statistical variation coefficient (the value S / d obtained by dividing the standard deviation S by the diameter d in the distribution represented by the diameter when the projected area is approximated by a circle) is 20.
% Or less is preferred. Further, two or more tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion to be used in the present invention is described by P. Glafkides, Shimmy e Physique.
Photographeq (Chimie er Physique Photographeq
ue) (Paul Montell, 1967), GFDuffin, Photographic Emulsion Chemistry (Photographic EmulsionChe)
mistry) (Focal Press, 1966), Buoy
VLZelikman et al., Making
It can be prepared by a method described in, for example, Making and Coating Photographic Emulsion (Focal Press, 1964).

In forming the silver halide grains, a silver halide solvent such as ammonia, rodancali, rodanammonium, or the like may be used to control the growth of the grains.
Thioether compounds (eg, US Pat. No. 3,271,1
No. 57, No. 3,574, 628, No. 3,704,
No. 130, No. 4,297,439, No. 4,27
No. 6,374, etc.) and thione compounds (for example,
Nos. 144443, 53-82408, 55-7
7737 etc.), amine compounds (for example,
No. 100717) can be used. In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be coexisted.

As a binder or protective colloid which can be used in the emulsion layer or the intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sodium alginate;
Various sugar derivatives such as starch derivatives; mono- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Synthetic hydrophilic polymeric substances can be used. As gelatin, besides general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japan Society of Science Photography (Bull. Soc. Phot. Japan), No. 1
Enzyme-treated gelatin as described in pages 6, 30 (1966) may be used, or a hydrolyzate of gelatin may be used.

In the light-sensitive material of the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples thereof include chromium salts, aldehyde salts (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol-based compounds (dimethylol urea, etc.). Active halogen compounds (such as 2,4-dichloro-6-hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis ( Vinylsulfonylacetamide) ethane, bis (vinylsulfonylmethyl) ether or a vinyl polymer having a vinylsulfonyl group in the side chain, etc.) are preferable because they can quickly cure a hydrophilic colloid such as gelatin and provide stable photographic properties. N-carbamoylpyridinium salts ((1-
Morpholinocarbonyl-3-pyridinio) methanesulfonate and the like and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfate) also have fast curing rates and are excellent.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes 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. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, the pyrroline nucleus is an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus,
An oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, applicable indolenine nucleus, benzindolenine nucleus, indole nucleus, Benzuokisa zone Lumpur nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus. These nuclei may have a substituent on a carbon atom. In a merocyanine dye or a complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidin-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, an aminostilbenzene compound substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), formaldehyde condensation of an aromatic organic acid (Eg, US Pat. No. 3,743,743)
510), cadmium salts, azaindene compounds and the like. US Patent 3,615,6
No.13, No.3,615,641, No.3,617,29
The combinations described in JP-A Nos. 5 and 3,635,721 are particularly useful.

The silver halide photographic emulsion used in the present technology contains various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Can be done. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, and aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes) and pentaazaindenes ; Benzenethiosulfonate, benzenesulfonic fins acid, known as antifoggants or stabilizers such as benzenesulfonic acid amide, can be added to many compounds.

The light-sensitive material of the present invention comprises a coating aid, an antistatic
One or more surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (eg, accelerating development, increasing contrast, sensitizing).

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes,
Azo dyes are preferably used, in addition to cyanine dyes,
Azomethine dyes, triarylmethane dyes and phthalocyanine dyes are also useful. The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on a support. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of arrangement of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive layers, blue-sensitive layer, green-sensitive layer and red-sensitive layer or in order of blue-sensitive, red-sensitive and green-sensitive layers. Any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the reaching sensitivity.
The three-layer structure may further improve the graininess. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer of fine silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity. Generally, the cyan-sensitive coupler is contained in the red-sensitive emulsion layer, the magenta-forming coupler is contained in the green-sensitive emulsion layer, and the yellow-forming coupler is contained in the blue-sensitive emulsion layer. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

Various color couplers can be used in the photographic material of the present invention, and specific examples thereof are described in Research Disclosure (RD) No. 17643, VII-
It is described in the patents described in C to G. As the yellow coupler, for example, US Pat. No. 3,933,501
No. 4,022,620, No. 4,326,02
No. 4, No. 4,401,752, JP-B-58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760 are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferred. For example, US Pat. Nos. 4,310,619 and 4,351,8
No. 97, EP 73,636, U.S. Pat.
Nos. 61,432 and 3,725,067, Research Disclosure No. 24220 (June 1984)
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630.
No. 4,540,654 are preferred. Examples of cyan couplers include phenol-based and naphthol-based couplers.
No. 2,212, No. 4,146,396, No. 4,2
No. 28,233, No. 4,296,200, No. 2,
No. 369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308,
Nos. 4,334,011, 4,327,173
No. 3,329,729, EP 121,365A, U.S. Pat. No. 3,446,622.
No. 4,333,999 and 4,451,55
No. 9, No. 4,427,767, European Patent No. 161,
No. 626A is preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described, for example, in Research Disclosure No. 17643, section VII-G, US Pat.
No. 3,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Patent 1,146,368 are preferred.

Examples of couplers in which a coloring dye has an appropriate diffusibility include, for example, US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,57.
No. 0 and West German Patent (Publication) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
Nos. 0,211 and 4,367,282, and British Patent No. 2,102,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the same as described above for R
Patent No. D17643, Sections VII to F
Nos. 7-151944, 57-154234, 60
Preferred are those described in U.S. Pat. No. 4,248,962. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent Nos. 2,097,140 and 2,131,1.
No. 88, JP-A Nos. 59-157638 and 59-170
No. 840 is preferred.

Other couplers usable in the light-sensitive material of the present invention include, for example, US Pat.
No. 27, etc., US Patent No. 42834.
No. 72, No. 4,338,393, No. 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950.
Redox compounds or DIR coupler releasing couplers described in JP-A-62-24252, couplers releasing dyes capable of recoloring after release described in EP 173302A, R.C. D. No. 11449, 2424
1, bleach accelerator releasing couplers described in JP-A-61-201247 and the like, and ligand releasing couplers described in U.S. Pat. No. 4,553,477.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. An example of a high boiling solvent used in the oil-in-water dispersion method is disclosed in US Pat.
No. 7, etc. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Screw (2,
4-di-t-amylphenyl) phthalate, bis (2,
4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate,
Tridodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate), benzoates (eg, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides ( For example, N, N-diethyldodecaneamide, N, N-diethyllauramide,
N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,
4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg, , N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, and the like.
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are made of a flexible support such as plastic film, paper, cloth or the like or a rigid support such as glass, pottery, metal or the like which is usually used for the photographic light-sensitive material. Applied to the body. Those useful as flexible supports include films, baryta layers or α-olefin polymers composed of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate. (Eg, polyethylene, polypropylene, ethylene / butene copolymer)
And the like are coated or laminated paper. The support may be colored using a dye or a pigment. It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with a photographic emulsion layer or the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating and extrusion coating can be used. US Patent No. 2 if required
Nos. 681294, 2761791 and 3526
Multiple layers may be simultaneously coated by the coating method described in JP-A-528 and JP-A-3508947.

The present invention can be applied to various color and black-and-white photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color paper, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat developable color photosensitive materials. it can. Research Disclosure, No.
17123 (July 1978), or by using a three-color coupler mixture, or as described in U.S. Pat.
The present invention can be applied to black-and-white light-sensitive materials such as those for X-rays by utilizing black color couplers described in U.S. Pat. No. 26,461 and British Patent No. 2,102,136. Plate making films such as squirrel film or scanner film, X-ray films for direct / indirect medical or industrial use, negative black-and-white film for photography, black-and-white photographic paper, CO
The present invention can also be applied to M or ordinary microfilms, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials.

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, a peeling (peel apartment) type or JP-B-46-16356, JP-B-48-33697,
JP-A-50-13040 and British Patent 1,330,
A film unit of an integral type as described in JP-A No. 524 and a peel-free type film unit as described in JP-A-57-119345 can be employed. The use of a polymeric acid layer protected by a neutralization timing layer in any of the above formats is advantageous for widening the processing temperature latitude. When used in color diffusion transfer photography, it may be used by adding it to any layer in the light-sensitive material, or may be used by being sealed in a processing solution container as a developing solution component.

Various exposure means can be used for the light-sensitive material of the present invention. Any light source that emits a broad ray corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury lamps, fluorescent lamps, and strobe or metal-burning flash bulbs are common. A gas, dye solution or semiconductor laser that emits light in the wavelength range from ultraviolet to infrared,
Light emitting diodes and plasma light sources can also be used as recording light sources. Also, a phosphor screen (such as a CRT) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
Exposure means in which a linear or planar light source is combined with a micro-shutter array using D) or lanthanum-doped lead titanium zirconate (PLZT) can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but P-phenylenediamine compounds are preferably used. Typical examples thereof include 3-methyl-4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These diamines are generally more stable in a salt than in a free state, and are preferably used.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide,
It generally contains a development inhibitor or an antifoggant such as iodide, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, preservatives such as hydroxylamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dyes Forming couplers, competing couplers, nucleating agents such as sodium boron hydride, 1-phenyl-3-
Auxiliary developing agents such as pyrazolidone, viscosity-imparting agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, West German Patent Application (OLS) No. 2,622 , 95
The antioxidant described in No. 0 may be added to the color developer.

In the development process of the reversal color photosensitive material, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone,
Known black-and-white developers such as 3-pyrazolidones such as -phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. In order to further speed up the processing, a processing method of performing a bleach-fixing process after the bleaching process may be used. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV), and copper (II), peracids, quinones, and nitrone compounds are used. Ferricyanide; dichromate; iron (II) as a typical bleach
Organic complex salts of I) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid or citric acid, tartaric acid, malic acid, etc. Complex salts of organic acids; persulfates; manganates; nitrosophenols and the like can be used. Of these, iron (III) ethylenediaminetetraacetate,
Diethylenetriaminepentaacetate iron (III) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Further, the ethylene (III) complex salt of ethylenediaminetetraacetate is particularly useful in an independent bleaching solution or a single-bath bleach-fixing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 37
No. 418, No. 53-65732, No. 53-72623
Nos. 53-95630, 53-95631, 53-104232, 53-124424, and 5
Nos. 3-141623 and 53-28426, Research Disclosure No. 17129 (July 1978
Compounds having a mercapto group or a disulfide group described in JP-A-50-14129; a thiazolidine derivative as described in JP-A-50-140129;
JP-A-52-20832 and JP-A-53-32735.
Thiourea derivatives described in U.S. Patent No. 3,706,561; West German Patent No. 1,127,715;
Iodides described in JP-A-16235; West German Patent No. 966,4
Polyethylene oxides described in JP-A Nos. 10 and 2,748,430; Polyamine compounds described in JP-B-45-8836;
-59644, 53-94927, 54-35
Nos. 727, 55-26506 and 58-163
Compounds described in No. 940 and iodine and bromide ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858 and West German Patent 1,29.
0,812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective. Examples of the fixing agent include thiosulfate, thiocyanate, thioether-based compound thioureas, and a large amount of iodide, and thiosulfate is generally used. As a preservative for the bleach-fixing solution or the fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

After the bleach-fixing process or the fixing process, a washing process and a stabilizing process are usually performed. In the washing step and the stabilizing step, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water hardeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, fungicides for preventing the generation of various bacteria, algae and fungi, and antibacterial agents are used. Agents, metal salts typified by magnesium salts and aluminum salts and bismuth salts, surfactants for preventing drying load and unevenness, and various hardeners can be added as necessary. Or West, Photographic Science and Engineering Magazine (L.
E. West, Phot. Sci. Eng.), Volume 6, 344-359.
The compounds described on page (1965) and the like may be added. In particular, the addition of a chelating agent or an anti-binder is effective.

In the water washing step, two or more tanks are washed with countercurrent water.
It is common to save water. Further, instead of the water washing step, a multi-stage countercurrent stabilizing step as described in JP-A-57-8543 may be carried out. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds other than the above-mentioned additives are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, etc.) for adjusting the membrane pH (for example, pH 3 to 9) Aldehydes such as monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin can be mentioned as typical examples. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzoisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners, etc., may be used. These may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate and the like as a membrane pH adjuster after the treatment. In the color light-sensitive material for photographing, the step (washing-stabilization) usually performed after fixing can be replaced with the above-mentioned stabilizing step and washing step (water saving processing). At this time, when the amount of the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed. The washing and stabilizing treatment time of the present invention varies depending on the type of photosensitive material and the treatment conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. Nos. 3,342,597, Schiff base-type compounds described in 3,342,599, Research Disclosure No. 14850 and No. 15159, aldol compounds described in No. 13924, and the like. In addition to the metal salt complexes described in U.S. Pat. No. 3,719,492, urethane compounds described in JP-A-53-135628, JP-A-56-6235 and JP-A-56-235.
No. 16133, No. 56-59232, No. 56-678
No. 42, No. 56-87334, No. 56-83735
Nos. 56-83736, 56-89735, 56-81837, 56-54430, 56-
No. 106241, No. 56-107236, No. 57-9
Examples of the precursor include various salt-type precursors described in Nos. 7531 and 57-83565. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-5-14447.
Nos. 7-111147, 58-50532, 58-
No. 50536, No. 58-50533, No. 58-505
Nos. 34, 58-50535 and 58-1154
No. 38, etc.

Various processing solutions in the present invention may be used at 10 ° C. to 50 ° C.
Used at ° C. A temperature of 33 ° C. to 38 ° C. is standard, but higher temperatures can accelerate the processing and shorten the processing time, and lower temperatures can achieve higher image quality and improved processing solution stability. it can. Further, in order to save silver in the photosensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed. A heater, a temperature sensor, a liquid level sensor, a circulating pump, a filter, a floating pig, a squeegee, and the like may be provided in the various treatment baths as needed. In the case of continuous processing, a certain finish can be obtained by using a replenisher for each processing liquid to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction and the like. When the light-sensitive material of the present invention is a color paper, it can be subjected to a bleach-fixing process, if necessary, even if it is a color photographic material for photography.

[0058]

【Example】

Example 1 The present invention will be specifically described below. An aqueous silver nitrate solution and an aqueous potassium bromide solution were added to the aqueous gelatin solution containing potassium bromide and ammonia at 60 ° C. with stirring while maintaining the silver potential at +20 mV with respect to the saturated calomel electrode by stirring. After the formation of particles, the mixture was desalted by flocculation, gelatin was added, and the pH and pAg were adjusted to 6.3 and 8.5, respectively. This silver bromide emulsion has a grain diameter of 0.1.
85 μm (111) face / (100) face ratio is 55/45
This is a monodisperse tetrahedral emulsion having a coefficient of variation in grain diameter of 12%. After the emulsion was divided into 6 parts, the temperature was raised to 60 ° C., and sensitizers shown in Table 1 were added to each of the emulsions for optimal chemical ripening. Thereafter, the following compounds were added, and the resultant was coated on a triacetylcellulose film support having an undercoat layer together with a protective layer by a simultaneous extrusion method. (1) Emulsion layer-Emulsion ... Emulsion shown in Table 1-Coupler

[0059]

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-Tricresyl phosphate-Stabilizer 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene-Coating aid sodium dodecylbenzenesulfonate (2) Protective layer-Fine particles of polymethyl methacrylate・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt ・ Gelatin These samples were exposed for sensitometry (1/100
Sec), and the following color development processing was performed.

The density of the treated sample was measured with a green filter. Table 1 shows the obtained photographic performance results. Further, the coated sample was placed in an atmosphere at 45 ° C. and a relative humidity of 80%.
After storage for days, the same color development processing was performed. The relative sensitivity is represented by the reciprocal of the exposure required to obtain an optical density of fog value + 0.2, and the value of sample 1 immediately after coating is set at 100. The developing treatment used here was performed at 38 ° C. under the following conditions. 1. Color development 2 minutes 45 seconds Bleaching 6 minutes 30 seconds 3. 3 minutes 15 seconds Fixing 6 minutes 30 seconds 5. Washing water 3 minutes and 15 seconds 6. Stable 3 minutes 15 seconds The composition of the processing solution used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-βhydroxyethylamino) -2 4.5 g -Methyl-aniline sulfate 1 liter by adding water

Bleaching solution Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium salt 130 g Glacial acetic acid 14 ml Add water to 1 liter

Fixer Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g

As shown in Table 1, the selenium sensitizer of the present invention has a lower fog generation than the conventionally well-known selenium sensitizer. The reaching sensitivity was almost the same. In addition, a favorable result was obtained in which the sensitivity was not significantly reduced when stored under high temperature and high humidity.

[0066]

[Table 1]

Example 2 To 1.2 l of a 3.0% by weight gelatin solution containing 0.06 mol of potassium bromide was added, while stirring, 30 ml of a 25% by weight aqueous ammonia solution, and the mixture was maintained at 75.degree. To the reaction vessel, 50 cc of a 0.3 mol silver nitrate solution and 50 cc of a halogen salt aqueous solution containing 0.063 mol of potassium iodide and 0.19 mol of potassium bromide were added over 3 minutes by a double jet method. Thus, nucleation was performed by obtaining silver iodobromide grains having a projected area circle equivalent diameter of 0.2 μm and a silver iodide content of 25 mol%. Then likewise 7
At 5 ° C., add 60 ml of aqueous ammonia solution and add 1.5 ml.
800 ml of a halogen salt solution containing 800 ml of molar silver nitrate, 0.375 mol of potassium iodide and 1.13 mol of potassium bromide
ml was added simultaneously by the double jet method over 80 minutes to form a first coating layer. The resulting emulsion grains were octahedral silver iodobromide emulsions having an average projected area circle equivalent diameter of 0.95 μm. (Iodide content: 25 mol%).

Subsequently, acetic acid was added for neutralization.
5 mol silver nitrate solution, 1.5 mol potassium bromide solution and 2 mol
% Gelatin solution is added to the mixer to form a first coating layer / second coating layer by forming a silver bromide shell (second coating layer).
Particles having a coating layer ratio of 1: 1 were obtained. The resulting grains were octahedral monodispersed core / shell emulsion grains having a circle equivalent diameter of 1.2 μm. The obtained emulsion was divided into 4 parts, heated to 56 ° C., the following sensitizing dyes I to III were added, the sensitizers shown in Table 2 were added, and then an aqueous solution of sodium thiosulfate (6 × 10 ⁻⁶ mol / mol AgX). Chloroauric acid (1.2 × 10 ^-5 mol / mol Ag)
Aqueous solution and potassium thiocyanate aqueous solution (4.0 × 10 ⁻⁴⁾
Mol / mol Ag), and the mixture was optimally aged. Next, a coating aid (sodium dodecylbenzenesulfonate) and a stabilizer (4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene), an antifoggant (1- (m-sulfophenyl) -5-mercaptotetrazole monosodium salt), an emulsion containing oil-1,2 and couplers 1-4, and a protective layer (gelatin, poly). Methyl methacrylate particles and H-1, S-1, and 2) were applied onto a triacetyl cellulose film support having an undercoat layer by a coextrusion method. Sensitizing dye I

[0069]

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Sensitizing dye II

[0071]

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Sensitizing dye III

[0073]

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Oil-1 Tricresyl phosphate Oil-2 Bis (2-ethylhexyl) phthalate coupler 1

[0075]

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Coupler 2

[0077]

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Coupler 3

[0079]

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Coupler 4

[0081]

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H-1

[0083]

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[0084]

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[0085]

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The samples were exposed to light through a yellow filter (for 1/100 second) and subjected to the same color development processing as in Example 1. After storing in an atmosphere of 45 ° C. and a relative humidity of 85% for 5 days, the same color developing treatment was performed. Measure the concentration of the processed sample with a red filter,
The results in Table 2 were obtained.

[0087]

[Table 2]

The relative sensitivity was determined by assuming that Sample 10 immediately after coating was 100. As is evident from Table 2, when the compound of the present invention was subjected to gold-sulfur-selenium sensitization, the generation of fog when obtaining almost the same sensitivity was smaller than that of the conventional compound, and Preferred results were obtained in that the sensitivity was not significantly reduced during storage.

Example 3 Potassium bromide, thioether (HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂
OH) and gelatin were added and dissolved, and a solution containing silver nitrate, potassium iodide, potassium bromide and K ₃ IrCl ₆ was added to the solution kept at 70 ° C. with stirring (3 × 10 ⁻⁶ mol / mol Ag). )
The mixed solution was added by a double jet method. After completion of the addition, the temperature was lowered to 35 ° C., soluble salts were removed by a conventional flocculation method, and then the temperature was raised again to 40 ° C., and 60 g of gelatin was added and dissolved to adjust the pH to 6.8. . The obtained tabular silver halide grains have an average diameter of 1.
25 μm, 0.17 μm thickness, average diameter / thickness ratio of 7.
4 and 3 mol% of silver iodide. In addition, pA at 40 ° C
g was 8.4.

After the emulsion was divided into 4 parts, the temperature was raised to 62 ° C. to raise the sensitizing dye anhydro-5,5′-dichloro-9-ethyl-3,3′-di (3-sulfopropyl) oxacarbocyanine. Hydroxide sodium salt (500mg
/ AgX1 mol) and potassium iodide (200 mg / AgX1
Mol), a sensitizer shown in Table 3 was added, and an aqueous solution of chloroauric acid (9 × 10 ⁻⁶ mol / mol AgX) and potassium thiocyanate (3.2 × 10 ⁻⁴ mol / mol AgX) were further added. And sodium thiosulfate aqueous solution (8 × 10 ^-6 mol / mol A)
gX) was added and chemically aged for 30 minutes. After completion of the chemical sensitization, 100 g of each emulsion (containing 0.08 mol of Ag) was added at 40 ° C.
And the following were sequentially added while stirring to prepare a solution.

4-hydroxy-6-methyl-1,3,3a, 73% 2cc-tetrazaindene C ₁₇ H ₃₅ —O— (CH ₂ CHO) ₂₅ —H 2% 2.2 cc potassium polystyrene sulfonate 2 % 1.6 Degree of polymerization = ca. 3000 2,4-Dichloro-6-hydroxy-s-tria 2% 3 cc sodium gin Co. The coating solution for the surface protective layer was sequentially added at 40 ° C. with stirring at 40 ° C. according to the following to prepare a solution. 14% aqueous gelatin solution 56.8 g Polymethyl methacrylate fine particles (average particle size 3.9 g, 3.0 μm) Emulsion Gelatin 10% 4.24 g

[0092]

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Phenoxyethanol 0.02 g

[0094]

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[0095] _{H 2 O 68.8cc C 8 H 17} -C 6 H 5 (OCH 2 CH 2) 2 CH 2 CH 2 SO 3 Na 4.3% 3cc above-obtained emulsion coating solution and surface Coating was carried out together with the coating solution for a protective layer on a polyethylene terephthalate film support by a simultaneous extrusion method so that the volume ratio at the time of coating was 103: 45. The amount of silver applied is 2.
5 g / m ² . These samples were exposed (1/100 second) through a yellow filter and an optical wedge using a sensitometer, and then exposed to an RD-III developer for an automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) at 35 ° C. After developing for 30 seconds, fixing, washing with water and drying were carried out by a conventional method, and the photographic sensitivity was measured. In an atmosphere of 50 ° C. and 80% relative humidity,
After storage for days, the same development processing was performed. The photographic sensitivity is represented by a relative value of a reciprocal of an exposure amount necessary to obtain an optical density of fog value + 0.2.
And As is evident from Table 3, the compound of the present invention contains
When used for sulfur-selenium sensitization, compared to conventional compounds
Preferable results were obtained in which the occurrence of fog was low, the arrival sensitivity was almost the same, and the decrease in sensitivity when stored under high temperature and high humidity was small.

[0096]

[Table 3]

[0097]

The compound of the present invention suppresses the occurrence of fog during selenium sensitization as compared with a conventionally known compound,
In addition, almost the same high sensitivity can be achieved, and a change in sensitivity when stored under high temperature and high humidity can be suppressed.

Claims (1)

(57) [Claims] 1. A silver halide photographic material comprising a silver halide emulsion selenium-sensitized with at least one compound represented by the following general formula (1). General formula (I) In the formula, R ₁ represents an aliphatic group, an aromatic group, a heterocyclic group, OR ₃ or NR ₄ R ₅ , R ₂ represents OR ₃ or NR ₄ R ₅ , and R ₃ , R ₄ and R ₅ represent Represents a hydrogen atom, an aliphatic group or an aromatic group.