JP3494318B2 - Silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. In particular, the present invention relates to a silver halide photographic light-sensitive material having high sensitivity, less fogging, and high contrast.

[0002]

2. Description of the Related Art A silver halide emulsion used in a silver halide photographic light-sensitive material is usually chemically sensitized with various chemical substances in order to obtain desired sensitivity, gradation and the like. As typical methods thereof, sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold sensitization, reduction sensitization, and various sensitization methods using combinations thereof are known. Of these,
The most widely used method is the gold-sulfur sensitization method using so-called unstable sulfur compounds and gold compounds, which are capable of purifying silver sulfide by reacting with silver ions.
afkides, Chimie et Physique Photographique (Paul
Published by Montel, 1987, 5th edition), edited by TH James, Th
e Theory of the Photographic Process (Macmillan, 1977, 4th edition), H. Frieser, Die Grundlagen
der Photographischen Prozesse mit Silber-halogeni
den (Akademische Verlagsgeselshaft, 1968 etc.

By the way, as a method for subjecting a silver halide emulsion to gold-sulfur sensitization, a method in which an unstable sulfur compound capable of reacting with the above-mentioned silver ions to form silver sulfide and a gold compound are separately added are generally used. The method is described in the above-mentioned reference materials and the Journal of the Photographic Society of Japan, Volume 50, No. 2, pp. 108 and after (198
7 years) and the Jounal of the Optical Society of Ameri
It is described in ca 39, Vol. 6, page 494 and after (1949). In these methods, chloroauric acid has been used as a gold compound, and thiourea compounds and thiosulfates have been used as unstable sulfur compounds. However, in the case of using these compounds, the degree of sensitivity increase obtained is insufficient, fog is likely to occur, the gradation is softened, and when the light-sensitive material is stored for a long period of time, fog There are various problems that the occurrence is remarkable, and a means for solving them has been strongly demanded.

On the other hand, as a method of gold sulfur sensitization using a gold compound other than chloroauric acid, Japanese Patent Publication No. 38-6447, Japanese Patent Publication No. 62-85239, Japanese Patent Publication No. 45-29274, Methods using the compounds disclosed in 4-267249 and JP-A-4-268550 have been known. However, none of these compounds showed sufficient action to solve the above problems.
The effect of the compounds disclosed in JP-A-4-67032, JP-A-4-75053 and JP-A-4-86649 is to improve the increase of fog and deterioration of graininess when the photosensitive material is aged for a long time. Is written. However, the compounds disclosed herein are produced as a result of adding a conventionally known compound to a silver halide emulsion, and are not particularly novel, and their effects are insufficient. there were.

[0005]

From the above, there has been a strong demand for the development of a light-sensitive material having high sensitivity and less fog and having a high contrast. It is an object of the present invention to provide a silver halide photographic material having high sensitivity, low fog and high contrast.

[0006]

The above objects have been achieved by the following. That is, a compound represented by the following general formula
It has been achieved by a silver halide photographic light-sensitive material characterized in that it has at least one silver halide emulsion layer containing a sensitized emulsion on a support. General formula (I)

[0007]

[Chemical 2]

In the formula, R ₁ , R ₂ and R ₃ are aliphatic hydrocarbon groups, aryl groups, heterocyclic groups, OR ₄ , SR ₅ or
N (R ₆ ) R ₇ is represented, and R ₄ , R ₅ , R ₆ and R ₇ are aliphatic hydrocarbon groups, aryl groups or heterocyclic groups. Y represents a halogen atom, SR ′ or R ″, R ′ represents an aliphatic hydrocarbon group or an aryl group, and R ″ represents a thioglucose residue.

Next, the general formula (I) will be described in detail. In the general formula (I), R ₁ , R ₂ , R ₃ , R ₄ ,
The aliphatic hydrocarbon group represented by R ₅ , R ₆ , R ₇ and R ′ is preferably one having 1 to 30 carbon atoms, and particularly a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. , An alkenyl group, an alkynyl group, and an aralkyl group. 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, alkynyl group and aralkyl group include methyl group, ethyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group and cyclopentyl group. , Cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, benzyl group and the like.

In the general formula (I), R ₁ , R ₂ ,
The aryl group represented by R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ′ is preferably one having 6 to 30 carbon atoms, particularly a monocyclic or condensed ring having 6 to 20 carbon atoms. And an aryl group such as a phenyl group and a naphthyl group. In the general formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R
_The heterocyclic group represented by ₆ , R ₇ and R ′ is a nitrogen atom,
3 containing at least one of oxygen atom and sulfur atom
It is a 10-membered saturated or unsaturated heterocyclic group. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, such as a pyridyl group, an imidazolyl group, a quinolyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group,
Examples thereof include a thiazolyl group, a thienyl group, a furyl group and a benzothiazolyl group.

Examples of the halogen atom represented by Y in the general formula (I) include a fluorine atom, a chlorine atom and a bromine atom. Examples of the thioglucose residue represented by R "in the general formula (I) include a thioglucose group, S-2,3,4,5-tetraacetyl-1-β-D.
-Represents a thioglucose group and the like. In the general formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ′ are
Each group represented by may be substituted. The following are mentioned as a substituent.

Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group,
Ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, allyl group, 2-butenyl group, 3-pentenyl group, etc.), alkynyl Group (eg, propargyl group, 3-pentynyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, 4-methylphenyl group, etc.), heterocyclic group ( For example, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group, etc.), alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, 2-naphthyloxy group, etc.) ), An amino group (for example, an unsubstituted amino group, a dimethylamino group, an ethylamino group, an anilino group, etc.), Shiruamino group (e.g., acetylamino group, benzoylamino group, etc.), a ureido group (e.g., 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 unsubstituted sulfamoyl group) , N, N-
Dimethylsulfamoyl group, N-phenylsulfamoyl group and the like), carbamoyl group (for example, unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group and the like), sulfonyl group (for example, mesyl group, Tosyl 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, formyl group, pivaloyl group etc.), acyloxy group (eg acetoxy group, benzoyloxy group etc.) ), Phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide group, etc.), alkylthio group (for example, methylthio group, ethylthio group, etc.), arylthio group (for example, phenylthio group, etc.), cyano group,
A sulfo group, a carboxy group, a hydroxy group, a mercapto group, a phosphono group, a nitro group, a sulfino group, an ammonio group (for example, a trimethylammonio group, etc.), a phosphonio group, a hydrazino group and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (I), preferably R ₁ ,
R ₂ and R ₃ represent an aliphatic hydrocarbon group, an aryl group, Y represents a halogen atom, SR ′ and R ″, R ′ represents an aliphatic hydrocarbon group and an aryl group, and R ″ represents a thioglucose residue. Represent. More preferably in the general formula (I), R ₁ and R
₂ , R ₃ is an aliphatic hydrocarbon group, Y is a halogen atom, S
R'represents R ", R'represents an aliphatic hydrocarbon group, and R"
Represents a thioglucose residue. Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

The compound represented by the general formula (I) is, for example,
Helvetica Chimica Acta Volume 56, pages 2405 and up (1973
), U.S. Pat.No. 3,661,959 and Chemisce Berichte.
It can be synthesized by a method similar to the method described in materials such as Volume 105, page 2985 and after (1972).

The compound of the present invention can be added after being dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides. The addition amount of the compound of the present invention is preferably 1 × 10 ⁻² to 1 × 10 ⁻⁸ mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ mol per mol of silver halide. .

In the present invention, it is also preferable to use a sulfur sensitizer together. Specifically, known destabilizing sulfur compounds such as thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, allylthiourea), rhodanines and the like are mentioned, and silver halides are included. About 10 ⁻⁷ to 10 ⁻² mol can be used per mol. In the present invention, it is also preferable to use a selenium sensitizer together. For example, the unstable selenium sensitizer described in JP-B-44-15748 is preferably used.

Specifically, for example, colloidal selenium, selenoureas (eg, N, N-dimethylselenourea, selenoureas, tetramethylselenourea), selenamides (eg, selenacetoaceside, N, N-dimethyl-). Selenobenzamide), selenoketones (eg, selenoacetone, selenobenzophenone), selenides (eg, triphenylphosphine selenide, diethyl selenide), selenophosphates (eg, tri-p
-Tolyl selenophosphate), selenocarboxylic acid and esters, and isoselenocyanate compounds, and about 10 ^-8 to 10 ^-3 mol can be used per mol of silver halide.

In the present invention, a reduction sensitizer can also be used in combination, and specifically, for example, stannous chloride, aminoiminomethanesulfinic acid, a hydrazine derivative, a borane compound (eg, dimethylamineborane). , Silane compounds and polyamine compounds. In the present invention, it is also preferable to use a tellurium sensitizer in combination, as the tellurium sensitizer used in the present invention, for example, JP-A-4-204640, 4-271341, 4-333043, and Japanese Patent Application No. Four-
129787, 4-185004, 4-330495, 4-333030
No. 5, No. 5-4203, No. 5-4204, No. 5-106977, No. 5-2869
Tellurium sensitizers described in No. 16 and the like are preferable.

Specifically, phosphine tellurides (eg, butyl-diisopropylphosphine telluride,
Tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (for example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride Bis (N-phenyl-N-methylcarbamoyl) telluride,
Bis (ethoxycarbonyl) telluride), telluroureas (eg, N, N′-dimethylethylene tellurourea, N,
N'-diphenylethylene tellurourea), telluroamides, tellurohydrazides, telluroesters and the like, and about 10 ^-8 to 10 ^-3 mol can be used per mol of silver halide.

The conditions for the chemical sensitization in the present invention include:
There is no particular limitation, but pAg is 6 to 11, preferably 7 to 10, pH is 4 to 10 and temperature is 4
It is 0 to 95 ° C, preferably 45 to 85 ° C.

Further, in the present invention, it is preferable to carry out chemical sensitization in the presence of a silver halide solvent.

Specifically, thiocyanates (eg, potassium thiocyanate) and thioether compounds (eg, US Pat. Nos. 3,021,215 and 3,271,157).
Japanese Patent Publication No. 58-30571, Japanese Patent Laid-Open No. 60-1367.
36, especially 3,6-dithia-1,8
Octanediol, etc., tetra-substituted thiourea compounds (for example, Japanese Patent Publication No. 59-11892, US Pat. No. 4,221,863)
Compound, especially tetramethylthiourea), and a thione compound described in JP-B-60-11341,
A mercapto compound described in JP-B-63-29727,
The mesoionic compound described in JP-A-60-163042, the selenoether compound described in U.S. Pat. No. 4,782,013, the telluroether compound described in JP-A-2-118566, and a sulfite salt can be mentioned. Among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used. The amount used is 10 ^-5 per mol of silver halide.
About 10 ^-2 mol 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.

The silver halide grains used in the present invention are:
Those having regular crystal forms such as cubes and octahedra, those having irregular crystal forms such as spheres and plates, or composite forms of these crystal forms It has. It is also possible to use a mixture of grains having various crystal forms, but 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 be composed of a uniform phase. A 2-structured particle having different iodine compositions between the inside of the particle and the surface layer (in particular, the iodine content inside is larger) is also preferable. Also, grains in which a latent image is mainly formed on the surface (eg, negative emulsion) may be used, and grains in which the latent image is mainly formed (eg, internal latent image type emulsion, pre-fogged direct reversal type emulsion) May be
Preferably, the particles are such that a latent image is mainly formed on the surface.

The silver halide emulsion used in the present invention is
Tabular grains having a thickness of 0.5 micron or less, preferably 0.3 micron or less and a diameter of preferably 0.6 micron or more, and grains having an average aspect ratio of 3 or more occupy 50% or more of the total projected area. Emulsions are also preferred.

The silver halide emulsion used in the present invention has a statistical coefficient of variation (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). A monodisperse emulsion having a ratio of 20% or less is particularly preferable. Further, two or more kinds of emulsions may be mixed.

The photographic emulsion used in the present invention is described by P. Glafkides, Shimmie et.
Chimie er
Physique Photographie)
(Published by Paul Montell, 1967), G. D. Duffin, Photographic Emulsion Chemistry (Photograph)
Hic Emulsion Chemistry (Focal Press, 1966), V.L. Zelikman et al., Making.
And Coating Photographic Emulsion (Making and Coating Pho
It can be prepared by using the method described in, for example, "Topographic Emulsion" (Focal Press, 1964).

Further, in order to control the growth of the silver halide grains when they are formed, as a silver halide solvent, for example, ammonia, rodancali, rodanammon,
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.
6,374), thione compounds (for example, JP-A-53-1).
No. 44319, No. 53-82408, No. 55-777.
37), amine compounds (for example, JP-A-54-1007).
No. 17) and the like can be used.

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt,
You may make an iron salt or an iron complex salt coexist.

As the binder or protective colloid that can be used in the emulsion layer or 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 polymer of gelatin and other polymers, albumin, casein protein; hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole. Various synthetic hydrophilic polymeric substances such as polyvinylpyrazole homo- or copolymers can be used.

As the gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin and the Japan Society for Photographic Science (Bul)
l. Soc. Photo. Japan), No. 16, 30
Enzyme-treated gelatin as described on page (1966) may be used, or a hydrolyzate of gelatin may be used.

The light-sensitive material of the present invention may contain an inorganic or organic hardener in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehyde salts (eg formaldehyde, glyoxal, glutaraldehyde) and N-methylol compounds (eg dimethylolurea). Active halogen compounds (eg 2,4-dichloro 6-hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (eg 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis ( Vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ether or vinyl-based polymer having a bitylsulfonyl group in the side chain) is preferable because it rapidly cures hydrophilic colloid such as gelatin and provides stable photographic characteristics. N-carbamoylpyridinium salts (eg (1-morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (eg 1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfonate) also cure Is faster and better.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. The 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 normally utilized by cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, the pyrroline nucleus is, for example, 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; 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, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus,
Benzoxadol nucleus, naphthoxazole nucleus, benzthiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,
A 4-dione nucleus, a rhodanine nucleus, and a 5- or 6-membered heterocyclic nucleus of a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic ring nuclear group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensation (For example, US Pat. No. 3,743,
No. 510), a cadmium salt, and an azaindene compound. U.S. Pat. No. 3,615,613
No. 3,615,641, No. 3,617,295
No. 3,635,721, the combination is particularly useful.

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

The light-sensitive material of the present invention comprises a coating aid, an antistatic agent,
One or more surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic characteristics (for example, development acceleration, hardening, sensitization).

The light-sensitive material produced 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. Such dyes include oxonol dyes, hexoxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes,
Azo dyes are preferably used, in addition to these, cyanine dyes,
Azomethine dyes, triarylmethine dyes and phthalocyanine dyes are also useful. The oil-soluble dye can be emulsified by the 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 the support.

Multilayer natural color color photographic materials usually have at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of arrangement of these layers can be arbitrarily selected as required. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive, blue-sensitive layer, green-sensitive and red-sensitive layers or blue-sensitive, red-sensitive and green-sensitive. Further, an emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity, or a three-layer structure to 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 different color sensitivity may be inserted between certain emulsion layers having the same color sensitivity. A sensitivity layer may be improved by providing a reflective layer of fine grain silver halide under the high sensitivity layer, especially the high sensitivity blue sensitive layer.

It is general that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler. You can also 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. Specific examples thereof include Research Disclosure (RD) No. 17643, VII-
It is described in the patents described in C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, Japanese Patent Publication No. 58-10739, British Patent No. 1,42
Those described in No. 5,020 and No. 1,476,760 are preferable.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds are preferable, for example, US Pat. Nos. 4,310,619 and 4,351,8.
97, European Patent 73,636, US Patent 3,0.
61,432, 3,725,067, Research Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630.
Nos. 4,540,654 are preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. For example, US Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4 are cited. , 296,200,
No. 2,369,929, No. 2,801,171
No. 2, No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
08, 4,334,011, 4,327,
No. 173, West German Patent Publication No. 3,329,729, European Patent 121,365A, US Patent No. 3,446,6.
No. 22, No. 4,333, 999, No. 4,451,
No. 559, No. 4,427,767, European Patent No. 16
Those described in No. 1,626A are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described, for example, in Research Disclosure No. 17643, Section VII-G, U.S. Pat. No. 4,16
Those described in 3,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Patent 1,146,368 are preferable.

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

Typical examples of polymerized dye-forming couplers are US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282 and British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
D17643, Patents described in paragraphs VII to F, JP-A-5
7-151944, 57-154234, 60
Those described in US Pat. No. 4,184,248 and US Pat. No. 4,248,962 are preferable.

Examples of the coupler which releases a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 2,
097,140, 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 41304.
Competitive couplers described in US Pat. No. 4,728,347.
2, multi-equivalent couplers described in JP-A Nos. 4338393 and 4310618, JP-A-60-185950,
DIR redox compounds or DIR coupler-releasing couplers described in JP-A No. 62-24252, couplers releasing a dye that restores color after separation described in EP 173302A, R.I. D. No. 11449, 24241,
Examples thereof include bleaching accelerator releasing couplers described in JP-A No. 61-201247, and ligand releasing couplers described in U.S. Pat. No. 4,553,477. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). , Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or Esters of phosphonic acids (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate). Over DOO, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (e.g., 2
-Ethylhexyne benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g. N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or Phenols (eg, isostearyl alcohol, 2,4-di-t
ert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), araline derivatives (eg, N, N) -Dibutyl-2
-Butoxy-5-tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). 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 are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxy. Examples include ethyl acetate and dimethylformamide.

The process, effects and specific examples of the latex for impregnation of the latex dispersion method are described in US Pat. No. 4,199,3.
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 flexible supports generally used for photographic light-sensitive materials such as plastic films, papers and cloths, or rigid supports such as glass, ceramics and metals. Applied to the body. Useful as flexible supports are, for example, cellulose nitrate,
Cellulose acetate, cellulose acetate butyrate, polystyrene,
It is a film made of a semi-synthetic or synthetic polymer of polyvinyl chloride, polyethylene terephthalate, or polycarbonate, a baryter layer or a paper coated or laminated with an α-olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with the photographic emulsion layers. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation or flame treatment 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 method, roller coating method, curtain coating method and extrusion coating method can be used. US Pat. No. 268 as required
No. 1294, No. 2761791, No. 352652
Multiple layers may be coated simultaneously by the coating methods described in No. 8 and No. 3508947.

The present invention can be applied to various color and black and white light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat developable color photosensitive materials. . Research Disclosure, No. 171
23 (July 1978) or by utilizing the tri-color coupler mix or in U.S. Pat. No. 4,126,46.
The present invention can be applied to a black-and-white light-sensitive material for X-rays or the like by utilizing the black color coupler described in No. 1 and British Patent No. 2,102,136. Film for film making such as lith film or scanner film, X-ray film for direct / indirect medical treatment or industrial, negative black and white film for photography, black and white photographic paper, COM or normal micro film, silver salt diffusion transfer type photosensitive material and The present invention can be applied to a printout type photosensitive material.

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, it is a peel-apart type or Japanese Patent Publication Nos. 46-16356 and 48-33697.
JP-A-50-13040 and British Patent 1,330,
An integrated type film unit as described in JP-A No. 524 and a peel-free type film unit as described in JP-A-57-119345 can be used.

The use of a polymeric acid layer protected by a neutralization timing layer in any of the above formats is advantageous in terms of broadening the processing temperature latitude. When used in the color diffusion transfer photographic method, it may be added to any layer in the light-sensitive material, or may be contained as a developing solution component in a processing solution container before use.

Various exposing means can be used for the light-sensitive material of the present invention. Any light source that emits a broad radiation corresponding to the sensitivity wavelength of the light-sensitive material can be used as an illumination light source or a writing light source. Flashlight sources such as natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common.

A gas, a dye solution or a semiconductor laser, a light emitting diode, or a plasma light source which emits light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a fluorescent surface (CRT, etc.) emitted from a fluorescent substance excited by an electron beam, liquid crystal (LCD), or lanthanum-doped lead titan zirconate (PLZ).
It is also possible to use an exposure means in which a linear or planar light source is combined with a micro shutter array utilizing T) or the like. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, an aminophenol compound is also useful, but a P-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline And their sulfates, hydrochlorides or p-toluenesulfonates. Salts of these diamines are generally more stable than those in the free state, and are preferably used.

The color developing solution contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a brominating agent,
It is common to include development inhibitors or antifoggants such as iodides, benzimidazoles, benzothiazoles or mercapto compounds. Also, if necessary,
Preservatives such as hydroxylamine or sulfite, organic solvents such as triethanolamine, diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, Typical examples are nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphenic acids and phosphonocarboxylic acids. Chelating agents such as the following, West German patent application (OLS) No. 2,622,950
The antioxidant described in No. 1 may be added to the color developing solution.

In the development processing of a reversal color light-sensitive material, black and white development is usually carried out before color development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone, 1
Known black-and-white developing agents 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 bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Examples of bleaching agents include iron (III)) and cobalt (II)
Compounds of polyvalent metals such as I), chromium (IV), and copper (II), peracids, quinones, and nitrone compounds are used. Ferricyanide as a typical bleaching agent; dichromate; iron (III)
Alternatively, an organic complex salt of cobalt (III), for example, an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid or an organic compound such as citric acid, tartaric acid, malic acid Acid complex salts; persulfates;
Manganese salt; nitrosophenol can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt,
Iron (III) diethylenetriaminepentaacetate and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in both the independent bleaching solution and the one-bath bleach-fixing solution.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP 53-32736, 53-57831, 37
No. 418, No. 53-65732, No. 53-72623.
No. 53, No. 53-95630, No. 53-95631, No. 53-104232, No. 53-124424, No. 5
No. 3-141623, No. 53-28426, Research Disclosure No. No. 17129 (July 1978)
A compound having a mercapto group or a disulfide group described in JP-A No. 50-140129, a thiazolidine derivative as described in JP-A No. 50-140129, and JP-B-45-8506.
Thiourea derivatives described in JP-A-52-20832, JP-A-53-32735 and US Pat. No. 3,706,561; West German Patent No. 1,127,715 and JP-A-58-1.
6235, iodide; West German Patent 966,410
And polyethylene oxides described in JP-A Nos. 2,748,430; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434 and 49-5.
No. 9644, No. 53-94927, No. 54-3572
No. 7, No. 55-26506 and No. 58-16394.
The compounds described in No. 0 and iodine and bromine ions can also be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858 and West German Patent 1,290,
The compounds described in JP-A No. 812 and JP-A-53-95630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds thioureas, and a large amount of iodides, but thiosulfates are generally used. As the bleach-fixing solution and the preservative for the fixing solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

After bleach-fixing treatment or fixing treatment, washing treatment and stabilizing treatment are usually carried out. Various known compounds may be added to the washing process and the stabilizing process for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, bactericides and antibacterial agents that prevent the formation of various bacteria, algae, and molds. An agent, a metal salt typified by a magnesium salt or an aluminum salt bismuth salt, a surfactant for preventing a dry load or rum, and various hardeners can be added if necessary. Or West's Photographic Science and Engineering magazine ((LE West, Photo. Sci. En.
g. ), Volume 6, pages 344 to 359 (1965), and the like, may be added. It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, two or more tanks are subjected to countercurrent water washing,
It is common to save water. Further, instead of the water washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be carried out. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. In addition to the above-mentioned additives, various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (eg borate, metaborate, etc.) for adjusting the membrane pH (eg pH 3-9).
Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Typical examples are aldehydes such as polycarboxylic acid used in combination) and formalin. In addition, if necessary, chelating agents (for example, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid), bactericides (for example, benzisothiazolinone, irithiazolone, 4 -Thiazoline benzimidazole, halogenated phenol,
Various additives such as a sulfanilamide, a benzotriazole), a surfactant, a brightening agent and a hardener may be used, and two or more kinds of the same or different target compounds 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, and ammonium thiosulfate as the film pH adjuster after the treatment.

Further, in the color photographic material for photographing, the (washing-stabilizing) step after fixing which is usually carried out can be replaced with the above-mentioned stabilizing step and washing step (water saving treatment). At this time, if the magenta coupler is 2 equivalents, the formalin in the stabilizing bath may be removed.

The washing and stabilizing treatment time of the present invention varies depending on the type of the photosensitive material and the treatment conditions, but is usually 20 seconds to 10 seconds.
Minutes, preferably 20 seconds to 5 minutes.

A color developing agent may be incorporated in the silver halide color light-sensitive material of the present invention for the purpose of simplifying and accelerating the processing. It is preferable to use various precursors of color developing agents for visceral use.

For example, indoaniline compounds described in US Pat. No. 3,342,597, and No. 3,342,599.
, Schiff base type compounds described in Research Disclosure 14850 and 15159, 1392
Aldol compounds described in US Pat. No. 3,719,
No. 492, metal salt complex salts, JP-A-53-13562
Including the urethane compounds described in JP-A-8,
6-6235, 56-16133, 56-59.
No. 232, No. 56-67842, No. 56-83734.
No. 56, No. 56-83735, No. 56-83736, No. 56-89735, No. 56-81837, No. 56-
54430, 56-106241, 56-10.
7236, 57-97531 and 57-83
Various salt type precursors described in No. 565 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
If necessary, various types of 1
-Phenyl-3-pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339 and JP-A-57-1.
44547, 57-211147, 58-50.
No. 532, No. 58-50536, No. 58-50533.
No. 58-50534, No. 58-50535 and No. 58-115438.

Various treatment liquids in the present invention are 10 ° C. to 50 ° C.
Used at ° C. A temperature of 33 ° C. to 38 ° C. is standard, but it is possible to increase the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can. Further, in order to save silver in the light-sensitive material, processing 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.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each processing bath.

Further, in the case of continuous treatment, a constant finish can be obtained by using a replenisher of each treatment liquid to prevent the liquid composition from varying. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

When the light-sensitive material of the present invention is a color paper, it can be bleach-fixed if necessary, and also when it is a color photographic material for photographing.

[0084]

EXAMPLES The present invention will be described in more detail with reference to specific examples below, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. Example 1 200 ml of an aqueous solution of silver nitrate (1M) and an aqueous solution of potassium bromide (1M) were added to 1 liter of an aqueous solution containing 0.9 g of potassium bromide kept at 75 ° C. and 35 g of gelatin and kept at pH 2.1 with nitric acid.
M) at the same time, the silver potential is -20 m against a saturated calomel electrode.
It was added for 20 minutes while keeping V. Thereafter, 200 ml of an aqueous silver nitrate solution (1M) and an aqueous potassium bromide solution (1M) were simultaneously added over 20 minutes while maintaining the silver potential at −20 mV with respect to the saturated calomel electrode. After the grain formation was completed, desalting and washing were carried out by a usual flocculation method, and gelatin and water were added to adjust pH to 6.5 and pAg to 8.4. The obtained silver bromide emulsion had a grain diameter of 0.25 μm and a variation coefficient of 13%.
Is a monodisperse octahedral emulsion.

This emulsion was divided into small portions, heated to 65 ° C. and kept warm, and the sensitizers and additives shown in Table 1 were added to the emulsion while stirring, followed by chemical ripening for 60 minutes. After that, gelatin, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, potassium poly-styrene sulfonate, and sodium dodecylbenzene sulfonate were added, and a triacetyl cellulose film support having an undercoat layer was added. On the body, gelatin, polymethylmethacrylate particles, 2,4-dichloro-6
-Co-extrusion method with a protective layer containing sodium hydroxy-s-triazine. For these samples,
After exposure for sensitometry (10 seconds) through an optical wedge, the MAA-1 developer of the following formulation was developed at 20 ° C for 10 minutes, and then stopped, washed with fixing water, and dried by a conventional method.
The optical density was measured.

[0086] MAA-1 developer 2.5 g of metol Ascorbic acid 10 g Nabox 35 g Potassium bromide 1 g Add water to 1 liter

[0087]

[Table 1]

The relative sensitivity was represented by the relative value of the reciprocal of the exposure amount required to obtain the optical density of the fog value + 0.2, and the sensitivity of Sample 1 was set to 100. The gradation γ (gamma) was determined from the photographic density that gives the fog of the characteristic curve +0.2, and the gradient to the photographic density of the fog +0.8. That is, a fog difference of 0.6 is fogged.
The relative exposure amount giving a photographic density of +0.8 minus the relative exposure amount giving a fog +0.2 was divided by the value.
As is clear from Table 1, when the compound of the present invention was added, high sensitivity was obtained, fog was reduced, and gradation became harder.

Example 2 (Color Development) In the same manner as in Example 1, a monodisperse silver bromide octahedral emulsion was prepared. This emulsion was divided into small portions, heated to 60 ° C., added with a sensitizer and additives as shown in Table 2, and chemically ripened for 60 minutes. Then magenta coupler; 3--3-2,4-di-t
ert-Amylphenoxy) butyrylamino benzoylamino-1- (2,4,6-trichlorophenyl) pyrazolone-5-
On, tricresyl phosphate, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetraazaindene, sodium poly-styrenesulfonate, sodium dodecylbenzenesulfonate, 1,2-bis (vinylsulfonylacetylamino) ethane are added to contain polymethylmethacrylate particles. It was coated by coextrusion with a gelatin protective layer onto a triacetyl cellulose film support having a subbing phase. These samples were exposed under an optical wedge (1/100
Second) and the following color development processing was performed. The density of the treated sample was measured with a green filter. The photographic properties obtained are shown in Table 2. The relative sensitivity was represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fog + 0.2, and the value of Sample 21 was set to 100. The gradation γ (gamma) was determined from the photographic density that gives the fog of the characteristic curve +0.2, and the gradient to the photographic density of the fog +0.8. That is, the difference in photographic density is 0.6
Is shown by the value obtained by subtracting the relative exposure amount which gives a photographic density of fog +0.8, and dividing the value.

(Color development processing method) Process processing time Processing temperature Color development 2 minutes 45 seconds 38 ℃ Bleach 3 minutes 00 seconds 38 ℃ Washing with water 30 seconds 34 ℃ Stationary 3 minutes 00 seconds 38 ℃ Washing with water (1) 30 seconds 24 ℃ Wash with water (2) 30 seconds 24 ℃ Stabilized 30 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃

Next, the composition of the treatment liquid will be described. (Color developer) (Unit: g)   Diethylenetriamine pentaacetic acid 1.0   1-hydroxyethylidene-1,1-diphosphonic acid 3.0   Sodium sulfite 4.0   Potassium carbonate 30.0   Potassium bromide 1.4   Potassium iodide 1.5mg   Hydroxylamine sulfate 2.4   4-N-ethyl-N-β-hydroxyethylamino -2-     Methylaniline sulfate 4.5   1.0 liter with water   pH 10.05

[0092] (Bleach) (Unit: g)   Ferric ethylenediaminetetraacetate sodium trihydrate 100.0   Ethylenediaminetetraacetic acid disodium salt 10.0   3-mercapto-1,2,4-triazole 0.08   Ammonium bromide 140.0   Ammonium nitrate 30.0   Ammonia water (27%) 6.5 ml   1.0 liter with water    pH 6.0

[0093] (Fixer) (Unit: g)   Ethylenediaminetetraacetic acid disodium salt 0.5   Ammonium sulfite 20.0   Ammonium thiosulfate aqueous solution (700 g / l) 290.0 ml   1.0 liter with water    pH 6.7

[0094] (Stabilizer) (Unit: g)    p- Toluene sodium sulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether     (Average degree of polymerization 10) 0.2   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazol-1-ylmethyl)     Piperazine 0.75   1.0 liter with water    pH 8.5

[0095]

[Table 2]

As is clear from Table 2, when the compound of the present invention was added, high sensitivity was obtained, fog was reduced, and gradation became harder.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 4-267249 (JP, A) JP 3-266828 (JP, A) JP 4-70650 (JP, A) JP 4- 96054 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/09

Claims (3)

(57) [Claims] 1. A compound represented by the following general formula (I) :
A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing a sensitized emulsion on a support. General formula (I) In the formula, R ₁ , R ₂ and R ₃ are an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, OR ₄ , SR ₅ or N (R ₆ ) R
₇ , R ₄ , R ₅ , R ₆ and R ₇ represent an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. Y is 'represents or R ", R' halogen atom, SR is or aliphatic hydrocarbon group
Or an aryl group, and R "represents a thioglucose residue. Wherein before following general formula (I) in R 'is an aliphatic carbon
The silver halide photographic light-sensitive material according to claim 1, which is a hydrogen halide group . 3. The emulsion contained in the silver halide emulsion layer is previously
The selenium compound together with the compound represented by the general formula (I)
Chemically sensitized by
Or the silver halide photographic light-sensitive material described in 2.