JPH0643576A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material which fogs less and has an excellent preservable property and high sensitivity by incorporating specific compds. into silver halide emulsion layers. CONSTITUTION:The silver halide emulsion subjected to selenium sensitization with at least one kind of the compds. expressed by formula are incorporated into the above-mentioned emulsion layers. In the formula, R1 denotes NR4(R5), SR6, SeR7, X, hydrogen atom; R2, R3 denote an aliphat. group, arom. group, heterocyclic group, OR8, -NR9(R10), SR11, SeR12, X, hydrogen atom. R4, R5, R9, R10 denote an aliphat. group, arom. group, heterocyclic group or hydrogen atom; R6 to R8, R11, R12 denote an aliphat. group, arom. group, heterocyclic group, hydrogen atom or cation; X denotes a halogen atom. Noble metal sensitizers, such as gold,. platinum, polladium and iridium, are preferably used in combination in such a case; more particularly preferably the gold sensitizer is used.

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 using a silver halide emulsion which has improved fog and sensitivity change during storage.

[0002]

2. Description of the Related Art A silver halide emulsion used for 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. In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, and rapid processing for accelerating the progress of development, and various improvements have been made to the sensitizing method. .
Among the above-mentioned sensitizing methods, selenium sensitizing method and tellurium sensitizing method are described in US Pat. Nos. 1,574,944 and 16025.
No. 92, No. 1623499, No. 3297446
Nos. 3,297,447, 3,332,0069, 3,408,196, 3,408,197, and 34.
No. 42652, No. 3420670, No. 35913.
No. 85, No. 3772031, No. 3531289, No. 3655394, French Patent No. 2093038,
No. 2093209, Japanese Patent Publication Nos. 52-34491, 52-34492, 53-295, and 57-22.
090, JP-A-59-180536 and JP-A-59-18.
No. 5330, No. 59-181337, No. 59-187.
No. 338, No. 59-192241, No. 60-1500.
No. 46, No. 60-151637, No. 61-24673.
No. 8, British Patent Nos. 255,846 and 86,1984.
No. 235211, No. 1121496, No. 129
5462, 1396696, Canadian Patent 800
958 and HE Spencer et al.,
Journal of Photographic Science (Jo
urnal of Photographic Science), Volume 31, 158-
It is disclosed on page 169 (1983) and the like.

[0003]

However, in general, selenium sensitization has a larger sensitizing effect than the sulfur sensitization generally performed in the art, but fog is large and it tends to be easily softened. There are many. Although many of the above-mentioned known patents improve these drawbacks, they have still obtained insufficient results, and a basic improvement for suppressing the occurrence of fog has been earnestly desired. Also,
Particularly, when the gold sensitization is used together with the sulfur sensitization or the selenium sensitization, a remarkable increase in sensitivity can be obtained, but at the same time, the fog also increases.
Compared with gold-sulfur sensitization, gold-selenium sensitization has a particularly large increase in fog and develops technology to suppress fog generation, especially development of selenium sensitizer with less sensitivity change during storage and less fog generation. Was strongly desired.

An object of the present invention is to provide a high-sensitivity silver halide photographic light-sensitive material having less fog and excellent storage stability.

[0005]

The above object includes a silver halide photographic light-sensitive material containing a selenium-sensitized halogenated emulsion with at least one compound represented by the following general formula (I). The sensitizing effect of selenium sensitization, which was difficult to achieve by conventional techniques, can be fully utilized. General formula (I)

[0006]

[Chemical 3]

In the formula, R ₁ is NR ₄ (R ₅ ), SR ₆ , SeR
₇ , X, a hydrogen atom, and R ₂ , R ₃ are an aliphatic group, an aromatic group, a heterocyclic group, OR ₈ , —NR ₉ (R ₁₀ ), SR ₁₁ ,
SeR ₁₂ , X, represents a hydrogen atom. R ₄ , R ₅ , R ₉ ,
R ₁₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Alternatively, it represents a cation, and X represents a halogen atom.

Next, the general formula (I) will be described in detail. In the general formula (I), R ₂ , R ₃ , R ₄ , R ₅ , R
_{6, R 7, R 8,} R 9, R 10, R 11, and the aliphatic group represented by R ₁₂ is preferably be of 1 to 30 carbon atoms, especially straight-chain having 1 to 20 carbon atoms A branched or cyclic alkyl group, alkenyl group, or alkynyl group. 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, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, provalgyl group, 3-pentynyl group and the like.

In the general formula (I), R ₂ , R ₃ , R ₄ ,
_{R 5, R 6, R 7} , R 8, R 9, R 10, R 11, and R ₁₂
The aromatic group represented by is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

In the general formula (I), R ₂ , R ₃ , R ₄ ,
_{R 5, R 6, R 7} , R 8, R 9, R 10, R 11, and R ₁₂
The heterocyclic group represented by is a saturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom,
Alternatively, it is an unsaturated heterocyclic group. These may be a single ring or may form a condensed ring with another aromatic ring or a heterocycle. The heterocyclic group is preferably 5 to
It is a 6-membered aromatic aromatic heterocyclic group, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a thiazolyl group, an imidazolyl group, and a benzimidazolyl group. In formula (I), the cations represented by R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ represent an alkali metal and ammonium. The halogen atom represented by X in the general formula (I) represents, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group may be substituted. The following are mentioned as a substituent. Examples of typical substituents include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, amino groups, acylamino groups, ureido groups, urethane groups, sulfonylamino groups, sulfamoyl groups, Carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoramide group, diacylamino group, imide group, alkylthio group, arylthio group, halogen atom, cyano group, sulfo group Group, carboxy group, hydroxy group, phosphono group, nitro group, phosphine selenoyl group, and heterocyclic group. These groups may be further substituted. When there are two or more substituents, they may be the same or different. R ₁ , R ₂ , R
₃ may combine with each other to form a ring together with a phosphorus atom, and R ₄ and R ₅ and R ₉ and R ₁₀ may combine with each other to form a nitrogen-containing heterocycle.

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this.

[0013]

[Table 1]

[0014]

[Table 2]

The compound represented by the general formula (I) can be generally synthesized by the following reaction. Reaction A

[0016]

[Chemical 4]

Reaction B

[0018]

[Chemical 5]

Reaction C

[0020]

[Chemical 6]

Specific examples are, for example,

Rocz. Chem., 34, 1675 (1960) Chem. Ber., 49, 63 (1961) Zh. Obshch. Khim., 36, 1240 (1966) Z. Naturforsch., Part B, 24, 179 ( 1969) Helv, Chim. Acta, 46, 2667 (1963) Dokl. Akad. Nauk SSSR, 163, 1397 (196).
5) Bull. Acad. Pol. Soc., Ser. Sci. Chem., 14, 21
7 (1966) Angew. Chem. (Inter. Ed.), 3,586 (1964) Bull. Acad. Pol. Sci., Ser. Sci. Chem., 14, 30
3 (1966) Chem. Commun., 913 (1969) Can. J. Chem., 46, 1415 (1968) Izv. Acad. Nauk SSSR, Ser. Khim., 464 (196).
9) Zh. Obohch. Khim., 36, 923 (1966) Zh. Obohch. Khim., 37, 959 (1966) Zh. Obohch. Khim., 39, 2265 (1969) Izv. Acad. Nauk SSSR, Ser. Khim., 1606 (196
7) Izv. Acad. Nauk SSSR, Ser. Khim., 169 (196)
9) Izv. Acad. Nauk SSSR, Ser. Khim., 622 (197)
0) It can be synthesized according to the method described in Helv. Chem. Acta, 49, 1000 (1966).

Up to now, no specific example of using the compound of the general formula (I) as a selenium sensitizer has been reported. Therefore, it was extremely difficult to predict the sensitizing effect, fog, and other photographic effects of these compounds,
A remarkable effect could be obtained by using the compound of the present invention. These selenium sensitizers used in the present invention,
The amount of the tellurium sensitizer used will vary depending on the selenium compound, tellurium compound, silver halide grains, chemical ripening conditions used, etc., but is generally 10 ^-8 to 10 ^-4 per mol of silver halide.
A molar amount, preferably about 10 ⁻⁷ to 10 ⁻⁵ mol, is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but pAg is 6 to 11, preferably 7 to 10, more preferably 7 to 9.5, and temperature is 40 to 9.
The temperature is 5 ° C, preferably 50 to 85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium together. 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 also preferable to use a sulfur sensitizer together. Specific examples thereof include known unstable sulfur compounds such as thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, allylthiourea, etc.) and rhodanines, and silver halides. About 10 ⁻⁷ to 10 ⁻² mol can be used per mol.

In the present invention, it is also possible to use a reduction sensitizer in combination, and specifically, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivative, borane compound, silane compound, polyamine compound, Etc.

In the present invention, selenium sensitization is preferably carried out in the presence of a silver halide solvent. Specifically, thiocyanates (for example, potassium thiocyanate, etc.), thioether compounds (for example, US Pat.
No. 021215, No. 3271157, Japanese Patent Publication No. 58-3
No. 0571, JP-A-60-136736 and the like, particularly compounds such as 3,6-dithia-1,8-octanediol) and tetra-substituted thiourea compounds (for example, JP-B-59-1).
1892, U.S. Pat. No. 4,221,863, etc., particularly tetramethylthiourea, etc.), and thione compounds described in JP-B-60-11341, JP-B-63.
-29727, mercapto compounds, JP-A-60
Examples include the mesoionic compound described in -163042, the selenoether compound described in U.S. Pat. No. 4,782,013, the telluroether compound described in Japanese Patent Application No. 63-173474, and a sulfite. 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.
A molar amount 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 with regular crystal shapes such as cubes and octahedra, and irregular shapes such as spheres and plates.
lar) crystal form, or a compound form of these crystal forms. 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. 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 has a thickness of 0.5 micron or less, preferably 0.3 micron or less and a diameter of preferably 0.6 micron or more,
Particles with an average aspect ratio of 5 or more account for 50% of the total projected area
An average grain emulsion that occupies the above or a statistical coefficient of variation (value S / d obtained by dividing standard deviation S by diameter d in the distribution represented by the diameter when the projected area is approximated by a circle) is 20.
A monodisperse emulsion having a ratio of not more than% is preferable. Further, two or more kinds of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is described by P. Glafkides, Shimmy E. Phizik.
Chimie er Physique Photographeq
ue) (published by Paul Montel, 1967), GFDuffin, Photographic EmulsionChe
mistry) (Focal Press, 1966), buoy
Making by VLZelikman et al.
It can be prepared by the method described in Making and Coating Photographic Emulsion (Focal Press, 1964) and the like.

In order to control the growth of the silver halide grains at the time of forming the silver halide grains, a silver halide solvent such as ammonia, rhodancali, rhodanammon,
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) and thione compounds (for example, JP-A-53)
No. 144319, No. 53-82408, No. 55-7.
7737), amine compounds (for example, JP-A-54-
No. 100717) and the like can be used. In the process 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 present together.

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, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example gelatin derivatives,
Graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives; various kinds such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Synthetic hydrophilic polymeric substances can be used. In addition to general-purpose lime-processed gelatin, acid-processed gelatin and the Japan Society for Science and Photography (Bull. Soc. Phot. Japan), No. 1
An enzyme-treated gelatin as described in pages 6, 30 (1966) may be used, or a hydrolyzate of gelatin may be used.

The photosensitive material of the present invention may contain an inorganic or organic hardener in any hydrophilic colloid layer constituting the photographic photosensitive layer or the back layer. Specific examples include chromium salts, aldehyde salts (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.). Active halogen compounds (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 ( Vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ether, vinyl polymers having a bitylsulfonyl group in the side chain, and the like) are preferable because they rapidly cure hydrophilic colloids such as gelatin and give stable photographic characteristics. N-carbamoylpyridinium salts ((1-
Morpholinocarbonyl-3-pyridinio) methanesulfonate and the like) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfonate and the like) also have a fast curing rate and are excellent.

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 used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, the pyrroline nucleus is an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus,
Oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, , Indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom. The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5 to 6-membered heterocyclic nucleus such as a rhodanine nucleus or 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, an azaindene compound, and the like. U.S. Pat. No. 3,615,6
No. 13, No. 3,615, 641, No. 3,617, 29
The combinations described in No. 5 and No. 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 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), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as tria Theindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc. ; 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 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, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes,
Azo dyes are preferably used, in addition to these, cyanine dyes,
Azomethine dyes, triarylmethane 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 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 arbitrary emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity,
The graininess may be further improved as a three-layer structure. 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 common to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases. 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 include Research Disclosure (RD) No. 17643, VII-mentioned above.
It is described in the patents described in C to G. Examples of yellow couplers include US Pat. No. 3,933,501.
No. 4,022,620, 4,326,02
4, No. 4,401,752, Japanese Patent Publication No. 58-107
39, British Patent Nos. 1,425,020 and 1,4
Those described in No. 76,760 are preferable.

As the magenta coupler, 5-pyrazolone type 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 (6 June 1984).
, 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, and examples thereof include US Pat.
No. 2,212, No. 4,146,396, No. 4,2
No. 28,233, No. 4,296,200, No. 2,
369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308,
No. 4,334,011, No. 4,327,173
, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, US Patent No. 3,446,622.
No. 4,433,999, 4,451,55
9, No. 4,427,767, European Patent 161,
Those described in No. 626A are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described, for example, in Research Disclosure No. 17643, Item VII-G, US 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 shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282 and British Patent No. 2,102,173.

A coupler which releases a photographically useful residue upon coupling is 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 couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patents 2,097,140 and 2,131,1.
88, JP-A-59-157638 and JP-A-59-170.
Those described in No. 840 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. 27,834, US Pat.
No. 72, No. 4338393, No. 4310618 and the like, multiequivalent couplers, JP-A-60-185950.
DIR redox compounds or DIR coupler releasing couplers described in JP-A No. 62-24252 and the like, couplers releasing a dye that restores color after separation described in EP 173302A, R.I. D. No. 11449, 2424
1, bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in oil-in-water dispersion methods are US Pat. No. 2,322,202.
No. 7, etc. Specific examples of the high-boiling 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 (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Screw (2,
4-di-t-amylphenyl) phthalate, bis (2,2
4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (for example, 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), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides ( For example, N, N-diethyldodecaneamide, N, N-diethyllaurylamide,
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 are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

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.
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 a flexible support commonly used for photographic light-sensitive materials such as a plastic film, paper, cloth or a rigid support such as glass, pottery or metal. Applied to the body. Useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, or polycarbonate, a variator layer or an α-olefin polymer. (For example, polyethylene, polypropylene, ethylene / butene copolymer)
It is a paper or the like coated or laminated with the above. 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 photographic emulsion layers and 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 undercoat 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 Patent No. 2 as required
No. 681294, No. 2761791, No. 3526
Multiple layers may be coated at the same time by the coating methods described in No. 528 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. it can. Research Disclosure, No.
17123 (July 1978) and the like, or by utilizing a three-color coupler mixture, or in US Pat.
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-forming coupler described in No. 26,461 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 printing paper, CO
The present invention can 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, 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 types of formats is advantageous for 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. Flash light 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. 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. In addition, a phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
D) or lanthanum-doped lead titan zirconate (PLZT) or the like may be used as an exposure means in which a linear or planar light source is combined with a microshutter array. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used for 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-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Examples thereof include 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 developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, bromide,
It generally contains a development inhibitor such as iodide, benzimidazoles, benzothiazoles or mercapto compounds or an antifoggant. 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, and dyes. Forming couplers, competitive 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 developing solution.

In the development processing of the reversal color light-sensitive material, black and white development is usually carried out and then color development is carried out. 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), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitrone compounds and the like are used. Ferricyanide as a typical bleaching agent; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or citric acid, tartaric acid, malic acid, etc. Complex salts of organic acids; persulfates; manganates; nitrosophenol and the like 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-baths.
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. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; and thiazolidine derivatives as described in JP-A No. 50-140129; JP-B-45-8506.
No. 52-20832 and 53-32735.
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, JP-A-58.
No. 16235, iodide; West German Patent No. 966,4.
No. 10 and No. 2,748,430; polyethylene oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434, JP-A-49434
-59644, 53-94927, 54-35.
727, 55-26506 and 58-163.
The compounds described in No. 940 and iodine and bromide 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 in particular, US Pat. No. 3,893,858 and West German Patent 1,29.
Compounds described in JP-A No. 0,812 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, and 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 the bleach-fixing treatment or the 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 magnesimu salt or aluminum salt bismuth salt, a surfactant for preventing drying load or unevenness, and various hardeners can be added as necessary. Or West by Photographic Science and Engineering (L.
E. West, Phot. Sci. Eng.), Volume 6, 344-359
The compounds described on page (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 (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting the membrane pH (for example, pH 3 to 9), Representative examples include aldehydes such as monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids used in combination) and formalin. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners and other various additives may be used, and two or more of the same or different target compounds may be used. You may use together above.

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 a film pH adjusting agent after the treatment. Further, in the case of the color photosensitive material for photographing, the (washing-stabilizing) step after fixing which is usually performed can be replaced with the above-mentioned stabilizing step and the washing step (water saving processing). 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 is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, though it varies depending on the type of the photosensitive material and the processing conditions.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. No. 3,342,597, Schiff base type compounds described in No. 3,342,599, Research Disclosure 14850 and No. 15159, aldol compounds described in No. 13924, Metal salt complexes described in U.S. Pat. No. 3,719,492, urethane compounds described in JP-A No. 53-135628, JP-A Nos. 56-6235 and 56-
16133, 56-59232, 56-678.
No. 42, No. 56-83734, No. 56-83735.
No. 56, No. 56-83736, No. 56-89735, No. 56-81837, No. 56-54430, No. 56-.
106241, 56-107236, 57-9.
Various salt type precursors described in, for example, No. 7531 and No. 57-83565 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A Nos. 56-64339, 57-144547 and 5
7-211147, 58-50532, 58-
No. 50536, No. 58-50533, No. 58-505.
34, 58-50535 and 58-1154.
No. 38 and the like.

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, the 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 treatment bath. Further, in the case of continuous processing, a constant finish can be obtained by using a replenisher for each processing solution 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. When the light-sensitive material of the present invention is a color paper, it can be generally bleach-fixed if necessary and when it is a color photographic material for photographing.

[0063]

【Example】

Example 1 The present invention is specifically described below. While stirring in a gelatin aqueous solution containing potassium bromide and ammonia kept at 60 ° C., a silver nitrate aqueous solution and a potassium bromide aqueous solution were added by a double jet method while keeping the silver potential at +20 mV against a saturated calomel electrode. After the completion of particle formation, desalting was carried out by the flocculation method and gelatin was added to adjust pH to 6.3 and pAg to 8.5. This silver bromide emulsion has a grain diameter of 0.
85μm (111) face / (100) face ratio is 55/45
And is a monodisperse tetradecahedral emulsion having a variation coefficient of grain diameter of 12%. After the emulsion was divided into 7 parts, the temperature was raised to 60 ° C., and then the sensitizers shown in Table 2 were added to each for optimum chemical ripening. Then, the compounds shown below were added and coated on a triacetyl cellulose film support having an undercoat layer together with the protective layer by the simultaneous extrusion method. (1) Emulsion layer ・ Emulsion ... Emulsion shown in Table 1 ・ Coupler

[0064]

[Chemical 7]

Tricresyl phosphate-stabilizer 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene-coating aid sodium dodecylbenzenesulfonate (2) protective layer-polymethylmethacrylate fine particles・ 2,4-Dichloro-6-hydroxy-s-triazine sodium salt ・ Gelatin These samples were exposed for sensitometry (1/100).
Second) and the following color development processing was performed.

The density of the treated sample was measured with a green filter. The results of the obtained photographic performance are shown in Table 3. In addition, the coated sample is placed in an atmosphere of 45 ° C. and 80% relative humidity for 5 minutes.
It was stored for a day and subjected to the same color development processing. The relative sensitivity was represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value + 0.2, and Sample 1 immediately after coating was set to 100. The developing treatment used here was carried out at 38 ° C. under the following conditions. 1. Color development 2 minutes 45 seconds 2. Bleach 6 minutes 30 seconds 3. Washing with water 3 minutes 15 seconds 4. Fixation 6 minutes 30 seconds 5. Washing with water 3 minutes 15 seconds 6. Stable 3 minutes 15 seconds The composition of the treatment liquid 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-β hydroxyethylamino) -2 4.5 g-Methyl-aniline sulfate water 1 liter

[0068]
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 Water is added to 1 liter

Fixing solution Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added to 1 liter

Stabilizer Formalin 8.0 ml Water is added to 1 liter As is clear from Table 3, the selenium sensitizer of the present invention is the same as the well-known selenium sensitizers (A) and (C). In comparison, the fog was low and the arrival sensitivity was almost the same. Moreover, compared with the sensitizer (B) having a low fog, the fog of the present invention is similar to the sensitizer (B), but is effective in a smaller amount, and the sensitivity is less decreased when stored under high temperature and high humidity. Very favorable results have been obtained.

[0071]

[Table 3]

Example 2 To 1.2 liters of a 3.0% by weight gelatin solution containing 0.06 mol of potassium bromide, 30 ml of a 25% by weight aqueous ammonia solution was added with stirring, and the mixture was kept at 75 ° C. To the reaction vessel, 50 cc of a 0.3 mol silver nitrate solution, 50 cc of a halogen salt aqueous solution containing 0.063 mol of potassium iodide and 0.19 mol of potassium bromide were added by the double jet method over 3 minutes. 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 7
At 5 ° C, add 60 ml of aqueous ammonia solution and add 1.5
800 ml of mol silver nitrate, 0.375 mol of potassium iodide and 1.13 mol of halogen salt solution containing potassium bromide 800
ml was simultaneously added by the double jet method over 80 minutes to form a first coating layer. The obtained 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 to the mixture to neutralize it.
5 molar silver nitrate solution and 1.5 molar potassium bromide solution and 2
The first coating layer / second coating layer is formed by adding a gelatin solution of wt% to the mixer to form a silver bromide shell (second coating layer).
Particles with a coating layer ratio of 1: 1 were obtained. The obtained grains were octahedral monodisperse core / shell emulsion grains having an equivalent circle diameter of 1.2 μm. The obtained emulsion was divided into 5 parts, and the mixture was heated to 56 ° C. and the sensitizing dyes I to III shown below were added and the sensitizers shown in Table 4 were added, followed by an aqueous sodium thiosulfate solution (6 × 10 ^-6 mol / mol AgX ), Chloroauric acid (1.2 × 10 ⁻⁵ mol / mol A
g) aqueous solution and potassium thiocyanate aqueous solution (4.0 × 1
^0-4 mol / mol Ag) was added, and the mixture was aged and sampled sequentially as shown in the table. Next, a coating aid (sodium dodecylbenzenesulfonate), a stabilizer (4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene), an antifoggant (1- (m-sulfophenyl)- 5
-Mercaptotetrazole monosodium salt), oil
-1, 2 and an emulsion containing couplers 1 to 4 were added, and a protective layer (gelatin, polymethylmethacrylate particles, and H-
1, S-1 and S-2) in a coextrusion method onto a triacetyl cellulose film support having a subbing layer. Sensitizing dye I

[0074]

[Chemical 8]

Sensitizing dye II

[0076]

[Chemical 9]

Sensitizing dye III

[0078]

[Chemical 10]

Oil-1 Tricresyl Phosphate Oil-2 Bis (2-ethylhexyl) phthalate Coupler 1

[0080]

[Chemical 11]

Coupler 2

[0082]

[Chemical 12]

Coupler 3

[0084]

[Chemical 13]

Coupler 4

[0086]

[Chemical 14]

H-1

[0088]

[Chemical 15]

[0089]

[Chemical 16]

[0090]

[Chemical 17]

These samples were exposed through a yellow filter (1/100 seconds) and subjected to the same color development process as in Example 1. The processed sample was subjected to concentration measurement with a red filter, and the results shown in Table 4 were obtained.

[0092]

[Table 4]

The relative sensitivity was 1 for Sample 10 aged for 56 minutes.
00 was obtained. As is clear from Table 4, when gold-sulfur-selenium sensitization was performed using the compound of the present invention, when almost the same ultimate sensitivity was obtained as compared with the conventional compounds (A) and (C). Of fog is small, and fog is small, but the aging process is slower than that of the compound (B), which has a rapid aging process. It is preferable for

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 of 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 the double jet method. After the addition was completed, the temperature was lowered to 35 ° C., soluble salts were removed by a conventional flocculation method, the temperature was raised again to 40 ° C., 60 g of gelatin was added and dissolved to adjust the pH to 6.8. . The tabular silver halide grains obtained had an average diameter of 1.
The thickness is 0.17 μm at 25 μ, and the average diameter / thickness ratio is 7.
4 and the silver iodide content was 3 mol%. PA at 40 ° C
The g was 8.4.

After dividing this emulsion into 5 parts, the temperature was raised to 62 ° C. and 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), the sensitizer shown in Table 5 is further added, and an aqueous solution of chloroauric acid (9 × 10 ⁻⁶ mol / mol AgX) and potassium thiocyanate (3.2 × 10 ⁻⁴ mol / mol AgX) are added. And sodium thiosulfate aqueous solution (8 × 10 ^-6 mol / mol A
gX) was added and chemically aged for 30 minutes. After the chemical sensitization, 100 g of each emulsion (containing 0.08 mol of Ag) was added at 40 ° C.
The solution was dissolved in, and the following were added sequentially with stirring to prepare a solution.

[0096] 4-hydroxy-6-methyl -1,3,3a, 7 3% 2cc - tetrazaindene _{C 17 H 35 -O- (CH 2} CHO) 25 -H 2% 2.2cc polystyrenesulfonic acid potassium 2 % 1.6 Degree of polymerization = ca. 3000 2,4-dichloro-6-hydroxy-s-tria 2% 3cc ginsodium The surface protection layer coating solution was sequentially added at 40 ° C. with stirring under to the following conditions to prepare a solution. 14% aqueous gelatin solution 56.8 g Polymethylmethacrylate fine particles (average particle size 3.9 g 3.0 μm) Emulsion gelatin 10% 4.24 g

[0097]

[Chemical 18]

Phenoxyethanol 0.02 g

[0099]

[Chemical 19]

H ₂ O 68.8 cc C ₈ H ₁₇ -C ₆ H ₅ (OCH ₂ CH ₂ ) ₂ CH ₂ CH ₂ SO ₃ Na 4.3% 3 cc Emulsion coating solution and surface obtained as above The coating solution for a protective layer was applied onto a polyethylene terephthalate film support by the simultaneous extrusion method so that the volume ratio at the time of application was 103: 45. The coated silver amount is 2.
It is 5 g / m ² . These samples were exposed (1/100 seconds) through a yellow filter and an optical wedge using a sensitometer, and were exposed to 35 ° C. with an RD-III developer for an automatic processor (manufactured by Fuji Photo Film Co., Ltd.). After being developed for 30 seconds, it was fixed, washed with water and dried by a conventional method, and the photographic sensitivity was measured. Also, in an atmosphere of 50 ° C and 80% relative humidity, 2
After storage for a day, the same development process was performed. The photographic sensitivity is represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog value + 0.2.
And As is clear from Table 5, the compound of the present invention, when used for gold-sulfur-selenium sensitization, has a lower fog generation than the conventional compounds (A) and (C), and is similar to the compound (B). The desired results were obtained such that the reaching sensitivity was almost the same and that the sensitivity decrease when stored under high temperature and high humidity was smaller than that of the compound (B).

[0101]

[Table 5]

[0102]

The compound of the present invention suppresses the occurrence of fog during selenium sensitization, as compared with the conventionally known compounds.
In addition, it is possible to stably achieve almost the same high sensitivity, and further it is possible to suppress a change in sensitivity when stored under high temperature and high humidity.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 26, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title of the invention Silver halide photographic light-sensitive material

[Claims]

[Chemical 1] In the formula, R ₁ represents NR ₄ (R ₅ ), SR ₆ , SeR ₇ , X, and a hydrogen atom, and R ₂ and R ₃ are aliphatic groups, aromatic groups, heterocyclic groups, OR ₈ , —NR ₉ (R ₁₀ ), SR ₁₁ , SeR ₁₂ ,
X represents a hydrogen atom. R ₄ , R ₅ , R ₉ , and R ₁₀ represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom, and R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ represent an aliphatic group, an aromatic group. Represents a group group, a heterocyclic group, a hydrogen atom or a cation,
X represents a halogen atom.

[Chemical 2] In the formula, R ₁ represents NR ₄ (R ₅ ), SR ₆ , SeR ₇ , X, and a hydrogen atom, and R ₂ and R ₃ are aliphatic groups, aromatic groups, heterocyclic groups, OR ₈ , —NR ₉ (R ₁₀ ), SR ₁₁ , SeR ₁₂ ,
X represents a hydrogen atom. R ₄ , R ₅ , R ₉ , and R ₁₀ represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom, and R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ represent an aliphatic group, an aromatic group. Represents a group group, a heterocyclic group, a hydrogen atom or a cation,
X represents a halogen atom.

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 using a silver halide emulsion which has improved fog and sensitivity change during storage.

[0002]

2. Description of the Related Art A silver halide emulsion used for 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. In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, and rapid processing for accelerating the progress of development, and various improvements have been made to the sensitizing method. .
Among the above-mentioned sensitizing methods, selenium sensitizing method and tellurium sensitizing method are described in US Pat. Nos. 1,574,944 and 16025.
No. 92, No. 1623499, No. 3297446
Nos. 3,297,447, 3,332,0069, 3,408,196, 3,408,197, and 34.
No. 42652, No. 3420670, No. 35913.
No. 85, No. 3772031, No. 3531289, No. 3655394, French Patent No. 2093038,
No. 2093209, Japanese Patent Publication Nos. 52-34491, 52-34492, 53-295, and 57-22.
090, JP-A-59-180536 and JP-A-59-18.
No. 5330, No. 59-181337, No. 59-187.
No. 338, No. 59-192241, No. 60-1500.
No. 46, No. 60-151637, No. 61-24673.
No. 8, British Patent Nos. 255,846 and 86,1984.
No. 235211, No. 1121496, No. 129
5462, 1396696, Canadian Patent 800
958 and HE Spencer et al.,
Journal of Photographic Science (Jo
urnal of Photographic Science), Volume 31, 158-
It is disclosed on page 169 (1983) and the like.

[0003]

However, in general, selenium sensitization has a larger sensitizing effect than the sulfur sensitization generally performed in the art, but fog is large and it tends to be easily softened. There are many. Although many of the above-mentioned known patents improve these drawbacks, they have still obtained insufficient results, and a basic improvement for suppressing the occurrence of fog has been earnestly desired. Also,
Particularly, when the gold sensitization is used together with the sulfur sensitization or the selenium sensitization, a remarkable increase in sensitivity can be obtained, but at the same time, the fog also increases.
Compared with gold-sulfur sensitization, gold-selenium sensitization has a particularly large increase in fog and develops technology to suppress fog generation, especially development of selenium sensitizer with less sensitivity change during storage and less fog generation. Was strongly desired.

An object of the present invention is to provide a high-sensitivity silver halide photographic light-sensitive material having less fog and excellent storage stability.

[0005]

The above object includes a silver halide photographic light-sensitive material containing a selenium-sensitized halogenated emulsion with at least one compound represented by the following general formula (I). The sensitizing effect of selenium sensitization, which was difficult to achieve by conventional techniques, can be fully utilized. General formula (I)

[0006]

[Chemical 3]

In the formula, R ₁ is NR ₄ (R ₅ ), SR ₆ , SeR
₇ , X, a hydrogen atom, and R ₂ , R ₃ are an aliphatic group, an aromatic group, a heterocyclic group, OR ₈ , —NR ₉ (R ₁₀ ), SR ₁₁ ,
SeR ₁₂ , X, represents a hydrogen atom. R ₄ , R ₅ , R ₉ ,
R ₁₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Alternatively, it represents a cation, and X represents a halogen atom.

Next, the general formula (I) will be described in detail. In the general formula (I), R ₂ , R ₃ , R ₄ , R ₅ , R
_{6, R 7, R 8,} R 9, R 10, R 11, and the aliphatic group represented by R ₁₂ is preferably be of 1 to 30 carbon atoms, especially straight-chain having 1 to 20 carbon atoms A branched or cyclic alkyl group, alkenyl group, or alkynyl group. 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, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, provalgyl group, 3-pentynyl group and the like.

In the general formula (I), R ₂ , R ₃ , R ₄ ,
_{R 5, R 6, R 7} , R 8, R 9, R 10, R 11, and R ₁₂
The aromatic group represented by is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

In the general formula (I), R ₂ , R ₃ , R ₄ ,
_{R 5, R 6, R 7} , R 8, R 9, R 10, R 11, and R ₁₂
The heterocyclic group represented by is a saturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom,
Alternatively, it is an unsaturated heterocyclic group. These may be a single ring or may form a condensed ring with another aromatic ring or a heterocycle. The heterocyclic group is preferably 5 to
It is a 6-membered aromatic aromatic heterocyclic group, and examples thereof include a pyridyl group, a furyl group, a thienyl group, a thiazolyl group, an imidazolyl group, and a benzimidazolyl group. In formula (I), the cations represented by R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ represent an alkali metal and ammonium. The halogen atom represented by X in the general formula (I) represents, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group may be substituted. The following are mentioned as a substituent. Examples of typical substituents include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, amino groups, acylamino groups, ureido groups, urethane groups, sulfonylamino groups, sulfamoyl groups, Carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoramide group, diacylamino group, imide group, alkylthio group, arylthio group, halogen atom, cyano group, sulfo group Group, carboxy group, hydroxy group, phosphono group, nitro group, phosphine selenoyl group, and heterocyclic group. These groups may be further substituted. When there are two or more substituents, they may be the same or different. R ₁ , R ₂ , R
₃ may combine with each other to form a ring together with a phosphorus atom, and R ₄ and R ₅ and R ₉ and R ₁₀ may combine with each other to form a nitrogen-containing heterocycle. R ₁ is NR ₄ (R ₅ ),
SR ₆ is preferred.

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

The compound represented by the general formula (I) can be generally synthesized by the reaction shown below. Reaction A

[0017]

[Chemical 4]

Reaction B

[0019]

[Chemical 5]

Reaction C

[0021]

[Chemical 6]

Specific examples include

Rocz. Chem., 34, 1675 (1960) Chem. Ber., 49, 63 (1961) Zh. Obshch. Khim., 36, 1240 (1966) Z. Naturforsch., Part B, 24, 179 ( 1969) Helv, Chim. Acta, 46, 2667 (1963) Dokl. Akad. Nauk SSSR, 163, 1397 (196).
5) Bull. Acad. Pol. Soc., Ser. Sci. Chem., 14, 21
7 (1966) Angew. Chem. (Inter. Ed.), 3,586 (1964) Bull. Acad. Pol. Sci., Ser. Sci. Chem., 14, 30
3 (1966) Chem. Commun., 913 (1969) Can. J. Chem., 46, 1415 (1968) Izv. Acad. Nauk SSSR, Ser. Khim., 464 (196).
9) Zh. Obohch. Khim., 36, 923 (1966) Zh. Obohch. Khim., 37, 959 (1966) Zh. Obohch. Khim., 39, 2265 (1969) Izv. Acad. Nauk SSSR, Ser. Khim., 1606 (196
7) Izv. Acad. Nauk SSSR, Ser. Khim., 169 (196)
9) Izv. Acad. Nauk SSSR, Ser. Khim., 622 (197)
0) It can be synthesized according to the method described in Helv. Chem. Acta, 49, 1000 (1966).

Up to now, no specific example of using the compound of the general formula (I) as a selenium sensitizer has been reported. Therefore, it was extremely difficult to predict the sensitizing effect, fog, and other photographic effects of these compounds,
A remarkable effect could be obtained by using the compound of the present invention. These selenium sensitizers used in the present invention,
The amount of the compound used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 10 ^-4 mol, preferably 10 ^-7 to 1 mol per mol of silver halide.
About 10 ^-5 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pAg is 6 to 1
1, preferably 7 to 10, more preferably 7 to 9.5, and the temperature is 40 to 95 ° C., preferably 50 to 8
It is 5 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium together. 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 also preferable to use a sulfur sensitizer together. Specific examples thereof include known unstable sulfur compounds such as thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, allylthiourea, etc.) and rhodanines, and silver halides. About 10 ⁻⁷ to 10 ⁻² mol can be used per mol.

In the present invention, it is also possible to use a reduction sensitizer in combination. Specifically, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, Etc.

Further, in the present invention, it is preferable to perform selenium sensitization in the presence of a silver halide solvent. Specifically, thiocyanates (for example, potassium thiocyanate, etc.), thioether compounds (for example, US Pat.
No. 021215, No. 3271157, Japanese Patent Publication No. 58-3
No. 0571, JP-A-60-136736 and the like, particularly compounds such as 3,6-dithia-1,8-octanediol) and tetra-substituted thiourea compounds (for example, JP-B-59-1).
1892, U.S. Pat. No. 4,221,863, etc., particularly tetramethylthiourea, etc.), and thione compounds described in JP-B-60-11341, JP-B-63.
-29727, mercapto compounds, JP-A-60
Examples include the mesoionic compound described in -163042, the selenoether compound described in U.S. Pat. No. 4,782,013, the telluroether compound described in Japanese Patent Application No. 63-173474, and a sulfite. 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.
A molar amount 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 with regular crystal shapes such as cubes and octahedra, and irregular shapes such as spheres and plates.
lar) crystal form, or a compound form of these crystal forms. 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. 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 has a thickness of 0.5 micron or less, preferably 0.3 micron or less and a diameter of preferably 0.6 micron or more,
Particles with an average aspect ratio of 5 or more account for 50% of the total projected area
An average grain emulsion that occupies the above or a statistical coefficient of variation (value S / d obtained by dividing standard deviation S by diameter d in the distribution represented by the diameter when the projected area is approximated by a circle) is 20.
A monodisperse emulsion having a ratio of not more than% is preferable. Further, two or more kinds of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is described by P. Glafkides, Shimmy e Physik.
Chimie er Physique Photographeq
ue) (published by Paul Montel, 1967), GFDuffin, Photographic EmulsionChe
mistry) (Focal Press, 1966), buoy
Making by VLZelikman et al.
It can be prepared by the method described in Making and Coating Photographic Emulsion (Focal Press, 1964) and the like.

Further, when forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rodancali, rodanmon,
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) and thione compounds (for example, JP-A-53)
No. 144319, No. 53-82408, No. 55-7.
7737), amine compounds (for example, JP-A-54-
No. 100717) and the like can be used. In the process 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 present together.

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, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example gelatin derivatives,
Graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives; various kinds such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Synthetic hydrophilic polymeric substances can be used. In addition to general-purpose lime-processed gelatin, acid-processed gelatin and the Japan Society for Science and Photography (Bull. Soc. Phot. Japan), No. 1
An 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 include chromium salts, aldehyde salts (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.). Active halogen compounds (2,4-dichloro-6-hydroxy-1,3,5-triazine and its sodium salt, etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis ( Vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ether, vinyl polymers having a vinylsulfonyl group in the side chain, etc.) are preferable because they rapidly cure hydrophilic colloids such as gelatin and give stable photographic characteristics. N-carbamoylpyridinium salts ((1-
Morpholinocarbonyl-3-pyridinio) methanesulfonate and the like) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfonate and the like) also have a fast curing rate and are excellent.

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 used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, the pyrroline nucleus is an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus,
Oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; nucleus in which alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which aromatic hydrocarbon ring is fused to these nuclei, that is, , Indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom. The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5 to 6-membered heterocyclic nucleus such as a rhodanine nucleus or 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 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, an azaindene compound, and the like. U.S. Pat. No. 3,615,6
No. 13, No. 3,615, 641, No. 3,617, 29
The combinations described in No. 5 and No. 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 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), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as tria Theindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc. ; 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 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, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes,
Azo dyes are preferably used, in addition to these, cyanine dyes,
Azomethine dyes, triarylmethane 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 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 arbitrary emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity,
The graininess may be further improved as a three-layer structure. 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 common to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases. 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 include Research Disclosure (RD) No. 17643, VII-mentioned above.
It is described in the patents described in C to G. Examples of yellow couplers include US Pat. No. 3,933,501.
No. 4,022,620, 4,326,02
4, No. 4,401,752, Japanese Patent Publication No. 58-107
39, British Patent Nos. 1,425,020 and 1,4
Those described in No. 76,760 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 (6 June 1984).
, 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, and examples thereof include US Pat.
No. 2,212, No. 4,146,396, No. 4,2
No. 28,233, No. 4,296,200, No. 2,
369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308,
No. 4,334,011, No. 4,327,173
, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, US Patent No. 3,446,622.
No. 4,433,999, 4,451,55
9, No. 4,427,767, European Patent 161,
Those described in No. 626A are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are described, for example, in Research Disclosure No. 17643, Item VII-G, US 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 shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282 and British Patent No. 2,102,173.

A coupler which releases a photographically useful residue upon coupling is 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 couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patents 2,097,140 and 2,131,1.
88, JP-A-59-157638 and JP-A-59-170.
Those described in No. 840 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. 27,834, US Pat.
No. 72, No. 4338393, No. 4310618 and the like, multiequivalent couplers, JP-A-60-185950.
DIR redox compounds or DIR coupler releasing couplers described in JP-A No. 62-24252 and the like, couplers releasing a dye that restores color after separation described in EP 173302A, R.I. D. No. 11449, 2424
1, bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in oil-in-water dispersion methods are US Pat. No. 2,322,202.
No. 7, etc. Specific examples of the high-boiling 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 (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Screw (2,
4-di-t-amylphenyl) phthalate, bis (2,2
4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (for example, 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), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides ( For example, N, N-diethyldodecaneamide, N, N-diethyllaurylamide,
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 are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation 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 film, paper and cloth, or rigid support such as glass, pottery and metal. Applied to the body. Useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, or polycarbonate, a variator layer or an α-olefin polymer. (For example, polyethylene, polypropylene, ethylene / butene copolymer)
It is a paper or the like coated or laminated with the above. 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 photographic emulsion layers and 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 undercoat 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 Patent No. 2 as required
No. 681294, No. 2761791, No. 3526
Multiple layers may be coated at the same time by the coating methods described in No. 528 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. it can. Research Disclosure, No.
17123 (July 1978) and the like, or by utilizing a three-color coupler mixture, or in US Pat.
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-forming coupler described in No. 26,461 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 printing paper, CO
The present invention can 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 peel (apartment) 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 types of formats is advantageous for 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. Flash light 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. 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. In addition, a phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
D) or lanthanum-doped lead titan zirconate (PLZT) or the like may be used as an exposure means in which a linear or planar light source is combined with a microshutter array. 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-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Examples thereof include 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 developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, bromide,
It generally contains a development inhibitor such as iodide, benzimidazoles, benzothiazoles or mercapto compounds or an antifoggant. 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, and dyes. Forming couplers, competitive 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 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), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitrone compounds and the like are used. Ferricyanide as a typical bleaching agent; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or citric acid, tartaric acid, malic acid, etc. Complex salts of organic acids; persulfates; manganates; nitrosophenol and the like 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. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; and thiazolidine derivatives as described in JP-A No. 50-140129; JP-B-45-8506.
No. 52-20832 and 53-32735.
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, JP-A-58.
No. 16235, iodide; West German Patent No. 966,4.
No. 10 and No. 2,748,430; polyethylene oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434, JP-A-49434
-59644, 53-94927, 54-35.
727, 55-26506 and 58-163.
The compounds described in No. 940 and iodine and bromide 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 in particular, US Pat. No. 3,893,858 and West German Patent 1,29.
Compounds described in JP-A No. 0,812 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, and 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 the bleach-fixing treatment or the 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 magnesimu salt or aluminum salt bismuth salt, a surfactant for preventing drying load or unevenness, and various hardeners can be added as necessary. Or West by Photographic Science and Engineering (L.
E. West, Phot. Sci. Eng.), Volume 6, 344-359
The compounds described on page (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 (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting the membrane pH (for example, pH 3 to 9), Representative examples include aldehydes such as monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids used in combination) and formalin. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners and other various additives may be used, and two or more of the same or different target compounds may be used. You may use together above.

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 a film pH adjuster after the treatment. Further, in the case of the color photosensitive material for photographing, the (washing-stabilizing) step after fixing which is usually performed can be replaced with the above-mentioned stabilizing step and the washing step (water saving processing). 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 is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, though it varies depending on the type of the photosensitive material and the processing conditions.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. No. 3,342,597, Schiff base type compounds described in No. 3,342,599, Research Disclosure 14850 and No. 15159, aldol compounds described in No. 13924, Metal salt complexes described in U.S. Pat. No. 3,719,492, urethane compounds described in JP-A No. 53-135628, JP-A Nos. 56-6235 and 56-
16133, 56-59232, 56-678.
No. 42, No. 56-83734, No. 56-83735.
No. 56, No. 56-83736, No. 56-89735, No. 56-81837, No. 56-54430, No. 56-.
106241, 56-107236, 57-9.
Various salt type precursors described in, for example, No. 7531 and No. 57-83565 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A Nos. 56-64339, 57-144547 and 5
7-211147, 58-50532, 58-
No. 50536, No. 58-50533, No. 58-505.
34, 58-50535 and 58-1154.
No. 38 and the like.

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, the 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 treatment bath. Further, in the case of continuous processing, a constant finish can be obtained by using a replenisher for each processing solution 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. When the light-sensitive material of the present invention is a color paper, it can be generally bleach-fixed if necessary and when it is a color photographic material for photographing.

[0064]

Example 1 The present invention will be specifically described below. While stirring in a gelatin aqueous solution containing potassium bromide and ammonia kept at 60 ° C., a silver nitrate aqueous solution and a potassium bromide aqueous solution were added by a double jet method while keeping the silver potential at +20 mV against a saturated calomel electrode. After the completion of particle formation, desalting was carried out by the flocculation method and gelatin was added to adjust pH to 6.3 and pAg to 8.5. This silver bromide emulsion has a grain diameter of 0.
85μm (111) face / (100) face ratio is 55/45
And is a monodisperse tetradecahedral emulsion having a variation coefficient of grain diameter of 12%. After the emulsion was divided into 7 parts, the temperature was raised to 60 ° C., and then the sensitizers shown in Table 2 were added to each for optimum chemical ripening. Then, the compounds shown below were added and coated on a triacetyl cellulose film support having an undercoat layer together with the protective layer by the simultaneous extrusion method. (1) Emulsion layer ・ Emulsion ... Emulsion shown in Table 1 ・ Coupler

[0065]

[Chemical 7]

Tricresyl phosphate-stabilizer 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene-coating aid sodium dodecylbenzenesulfonate (2) protective layer-polymethylmethacrylate fine particles・ 2,4-Dichloro-6-hydroxy-s-triazine sodium salt ・ Gelatin These samples were exposed for sensitometry (1/100).
Second) and the following color development processing was performed.

The density of the treated sample was measured with a green filter. The results of the obtained photographic performance are shown in Table 3. In addition, the coated sample is placed in an atmosphere of 45 ° C. and 80% relative humidity for 5 minutes.
It was stored for a day and subjected to the same color development processing. The relative sensitivity was represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value + 0.2, and Sample 1 immediately after coating was set to 100. The developing treatment used here was carried out at 38 ° C. under the following conditions. 1. Color development 2 minutes 45 seconds 2. Bleach 6 minutes 30 seconds 3. Washing with water 3 minutes 15 seconds 4. Fixation 6 minutes 30 seconds 5. Washing with water 3 minutes 15 seconds 6. Stable 3 minutes 15 seconds The composition of the treatment liquid 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-β hydroxyethylamino) -2 4.5 g-Methyl-aniline sulfate water 1 liter

[0069]
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 Water is added to 1 liter

Fixing solution Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added to 1 liter

Stabilizer Formalin 8.0 ml Water is added to 1 liter As is clear from Table 3, the selenium sensitizer of the present invention is the same as the well-known selenium sensitizers (A) and (C). In comparison, the fog was low and the arrival sensitivity was almost the same. Moreover, compared with the sensitizer (B) having a low fog, the fog of the present invention is similar to the sensitizer (B), but is effective in a smaller amount, and the sensitivity is less decreased when stored under high temperature and high humidity. Very favorable results have been obtained.

[0072]

[Table 4]

Example 2 To 1.2 liters of a 3.0% by weight gelatin solution containing 0.06 mol of potassium bromide, 30 ml of a 25% by weight aqueous ammonia solution was added with stirring, and the mixture was kept at 75 ° C. To the reaction vessel, 50 cc of 0.3 mol silver nitrate solution, 50 cc of an aqueous solution of halogen salt containing 0.063 mol of potassium iodide and 0.19 mol of potassium bromide were added by the double jet method over 3 minutes. 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 7
At 5 ° C, add 60 ml of aqueous ammonia solution and add 1.5
800 ml of mol silver nitrate, 0.375 mol of potassium iodide and 1.13 mol of halogen salt solution containing potassium bromide 800
ml was simultaneously added by the double jet method over 80 minutes to form a first coating layer. The obtained 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 to neutralize, and then 1.
5 molar silver nitrate solution and 1.5 molar potassium bromide solution and 2
The first coating layer / second coating layer is formed by adding a gelatin solution of wt% to the mixer to form a silver bromide shell (second coating layer).
Particles with a coating layer ratio of 1: 1 were obtained. The obtained grains were octahedral monodisperse core / shell emulsion grains having an equivalent circle diameter of 1.2 μm. The obtained emulsion was divided into 5 parts, and the mixture was heated to 56 ° C. and the sensitizing dyes I to III shown below were added and the sensitizers shown in Table 4 were added, followed by an aqueous sodium thiosulfate solution (6 × 10 ^-6 mol / mol AgX ), Chloroauric acid (1.2 × 10 ⁻⁵ mol / mol A
g) aqueous solution and potassium thiocyanate aqueous solution (4.0 × 1
^0-4 mol / mol Ag) was added, and the mixture was aged and sampled sequentially as shown in the table. Next, a coating aid (sodium dodecylbenzenesulfonate), a stabilizer (4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene), an antifoggant (1- (m-sulfophenyl)- 5
-Mercaptotetrazole monosodium salt), oil
-1, 2 and an emulsion containing couplers 1 to 4 were added, and a protective layer (gelatin, polymethylmethacrylate particles, and H-
1, S-1 and S-2) in a coextrusion method onto a triacetyl cellulose film support having a subbing layer. Sensitizing dye I

[0075]

[Chemical 8]

Sensitizing dye II

[0077]

[Chemical 9]

Sensitizing dye III

[0079]

[Chemical 10]

Oil-1 Tricresyl Phosphate Oil-2 Bis (2-ethylhexyl) phthalate Coupler 1

[0081]

[Chemical 11]

Coupler 2

[0083]

[Chemical 12]

Coupler 3

[0085]

[Chemical 13]

Coupler 4

[0087]

[Chemical 14]

H-1

[0089]

[Chemical 15]

[0090]

[Chemical 16]

[0091]

[Chemical 17]

These samples were exposed through a yellow filter (1/100 second) and subjected to the same color development process as in Example 1. The processed sample was subjected to concentration measurement with a red filter, and the results shown in Table 4 were obtained.

[0093]

[Table 5]

The relative sensitivity is 1 for Sample 10 aged for 56 minutes.
00 was obtained. As is clear from Table 4, when gold-sulfur-selenium sensitization was performed using the compound of the present invention, when almost the same ultimate sensitivity was obtained as compared with the conventional compounds (A) and (C). Of fog is small, and fog is small, but the aging process is slower than that of the compound (B), which has a rapid aging process. It is preferable for

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 of 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 the double jet method. After the addition was completed, the temperature was lowered to 35 ° C., soluble salts were removed by a conventional flocculation method, the temperature was raised again to 40 ° C., 60 g of gelatin was added and dissolved to adjust the pH to 6.8. . The tabular silver halide grains obtained had an average diameter of 1.
The thickness is 0.17 μm at 25 μ, and the average diameter / thickness ratio is 7.
4 and the silver iodide content was 3 mol%. PA at 40 ° C
The g was 8.4.

After dividing this emulsion into 5 parts, the temperature was raised to 62 ° C. and 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), the sensitizer shown in Table 5 is further added, and an aqueous solution of chloroauric acid (9 × 10 ⁻⁶ mol / mol AgX) and potassium thiocyanate (3.2 × 10 ⁻⁴ mol / mol AgX) are added. And sodium thiosulfate aqueous solution (8 × 10 ^-6 mol / mol A
gX) was added and chemically aged for 30 minutes. After the chemical sensitization, 100 g of each emulsion (containing 0.08 mol of Ag) was added at 40 ° C.
The solution was dissolved in, and the following were added sequentially with stirring to prepare a solution.

[0097] 4-hydroxy-6-methyl -1,3,3a, 7 3% 2cc - tetrazaindene _{C 17 H 35 -O- (CH 2} CHO) 25 -H 2% 2.2cc polystyrenesulfonic acid potassium 2 % 1.6 Degree of polymerization = ca. 3000 2,4-dichloro-6-hydroxy-s-tria 2% 3cc ginsodium The surface protection layer coating solution was sequentially added at 40 ° C. with stirring under to the following conditions to prepare a solution. 14% aqueous gelatin solution 56.8 g Polymethylmethacrylate fine particles (average particle size 3.9 g 3.0 μm) Emulsion gelatin 10% 4.24 g

[0098]

[Chemical 18]

Phenoxyethanol 0.02 g

[0100]

[Chemical 19]

H ₂ O 68.8 cc C ₈ H ₁₇ -C ₆ H ₅ (OCH ₂ CH ₂ ) ₂ CH ₂ CH ₂ SO ₃ Na 4.3% 3 cc Emulsion coating solution and surface obtained as above The coating solution for a protective layer was applied onto a polyethylene terephthalate film support by the simultaneous extrusion method so that the volume ratio at the time of application was 103: 45. The coated silver amount is 2.
It is 5 g / m ² . These samples were exposed (1/100 seconds) through a yellow filter and an optical wedge using a sensitometer, and were exposed to 35 ° C. with an RD-III developer for an automatic processor (manufactured by Fuji Photo Film Co., Ltd.). After being developed for 30 seconds, it was fixed, washed with water and dried by a conventional method, and the photographic sensitivity was measured. Also, in an atmosphere of 50 ° C and 80% relative humidity, 2
After storage for a day, the same development process was performed. The photographic sensitivity is represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog value + 0.2.
And As is clear from Table 5, the compound of the present invention, when used for gold-sulfur-selenium sensitization, has a lower fog generation than the conventional compounds (A) and (C), and is similar to the compound (B). The desired results were obtained such that the reaching sensitivity was almost the same and that the sensitivity decrease when stored under high temperature and high humidity was smaller than that of the compound (B).

[0102]

[Table 6]

Example 4 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was coated in multiple layers to prepare a sample 401 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 401) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³ HBS-1 0.20

Second Layer (Intermediate Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV -3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ⁻⁵ ExS-3 3 .1 × 10 ⁻⁴ ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.015 ExC-7 0.0050 ExC-8 0.02 Cpd-2 0.01 HBS- 1 0.040 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ⁻⁴ ExC-1 0.20 ExC-2 0.020 ExC-3 0.010 ExC-4 0.15 ExC-5 0.050 ExC-7 0.0050 ExC-8 0.025 Cpd-2 0.015 HBS- 1 0.060 Gelatin 1.00

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁴ ExS-3 3.4 × 10 ⁻⁴ ExC-1 0.097 ExC-2 0.010 ExC-3 0.035 ExC-6 0.020 ExC-8 0.030 HBS-1 0.22 HBS-2 0.10 Gelatin 1.30

Sixth Layer (Intermediate Layer) Cpd-1 0.040 HBS-1 0.020 Gelatin 0.80

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.30 ExS-4 2.6 × 10 ⁻⁵ ExS-5 1.8 × 10 ⁻⁴ ExS-6 6.9 × 10 ⁻⁴ ExM-1 0.021 ExM-2 0.26 ExM-3 0.030 ExY-1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.55 ExS-4 2.2 × 10 ⁻⁵ ExS-5 1.5 × 10 ⁻⁴ ExS-6 5.8 × 10 ⁻⁴ ExM-2 0.094 ExM-3 0.026 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.50

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 1.55 ExS-4 4.6 × 10 ⁻⁵ ExS-5 1.0 × 10 ⁻⁴ ExS-6 3.9 × 10 ⁻⁴ ExC-1 0.015 ExM-1 0.013 ExM-4 0.065 ExM-5 0.019 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54

10th Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.035 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.020 ExY-2 0.022 ExY-3 0.050 ExY− 4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth Layer (Medium Sensitivity Blue Sensitive Emulsion Layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ⁻⁴ ExC-7 7.0 × 10 ⁻³ ExY-2 0.050 ExY-30 .10 HBS-1 0.050 gelatin 0.78

Thirteenth Layer (High Sensitivity Blue Sensitive Emulsion Layer) Emulsion F Silver 0.70 ExS-7 2.8 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0 .69

Fourteenth Layer (First Protective Layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (diameter 1.7 μm) 0.10 B-30 .10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt, palladium salt, and rhodium salt.

[0120]

[Table 7]

In Table 7, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of Japanese Patent Application No. 2-34090. gave. Comparative compound A of Example 1 as emulsions A, B and D and comparative compound B as emulsions C, E and F as selenium sensitizers.
Sample No. 401-1 was prepared by using the above. On the other hand, Emulsion A prepared by using the compounds 3 and 32 of the present invention in combination as a selenium sensitizer
And B using Emulsions C and F with Compound 34 of the present invention, Emulsion D with Compounds 8 and 23 and 27 of the present invention, and Compound 25 of the present invention with Emulsion E. 401-2 was produced. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in Japanese Patent Application No. 2-34090 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0122]

[Chemical 20]

[0123]

[Chemical 21]

[0124]

[Chemical formula 22]

[0125]

[Chemical formula 23]

[0126]

[Chemical formula 24]

[0127]

[Chemical 25]

[0128]

[Chemical formula 26]

[0129]

[Chemical 27]

[0130]

[Chemical 28]

[0131]

[Chemical 29]

[0132]

[Chemical 30]

[0133]

[Chemical 31]

[0134]

[Chemical 32]

These samples were cut to a width of 35 mm and photographed by a camera, and the following treatment was carried out for 1 m ² per day for 15 days. Each processing was carried out as follows using an automatic processor FP-560B manufactured by Fuji Photo Film Co., Ltd. The treatment process and the treatment liquid composition are shown below.

(Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 17 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixed 50 seconds 38.0 ° C 420 ml 5 liters Water wash 30 seconds 38.0 ° C 980 ml 3.5 liters Stable (1) 20 seconds 38.0 ° C −3 liters Stable (2) 20 seconds 38.0 ° C 560 ml 3 liters Dry 1 minute 30 seconds 60 ° C * The replenishing amount is an amount per 1 m ² of the light-sensitive material. The stabilizing solution is a countercurrent system from (2) to (1), and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the washing process were each per 1 m ² of the light-sensitive material. 65 ml, 50 ml, 50 ml, 5
It was 0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N- (β- Hydroxyethyl) amino] aniline sulfate 4.5 6.0 Add water 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ferric Ammonium Monohydrate 130 195 Ammonium Bromide 70 105 Ammonium Nitrate 14 21 Hydroxyacetic Acid 50 75 Acetic Acid 40 60 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Liquid) A 15:85 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (P
H7.0)

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water was added 1.0 l 1 0.0 liter pH [prepared with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizing Solution) Common to Tank Solution and Replenishing Solution (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Disodium ethylenediaminetetraacetic acid Salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8. 5 After exposing Sample 401-1 and Sample 401-2 through a continuous wedge at a color temperature of 4800K for 1/100 seconds,
The above color development processing was performed and the optical density was measured. Samples 401-1 and 401-2 stored under the conditions of 40 ° C. and 80% relative humidity for 3 months were similarly exposed and processed. The change in fog density before and after storage for 3 months, the change in the logarithm of the exposure amount required to obtain an optical density of fog +0.2, and the change in the logarithm of the exposure amount required to obtain the optical density of fog +1.0 are displayed. -8. As is clear from Table-8, the compounds of the present invention showed favorable results that changes in fog and sensitivity were small during storage under high temperature and high humidity.

[0143]

[Table 8]

Example 5 Preparation of tabular grains 6 g of potassium bromide and 7 g of gelatin were added to 1 liter of water, and 37 cc of an aqueous solution of silver nitrate (4.00 g of silver nitrate) and potassium bromide were stirred into a container kept at 55 ° C. 38 cc of an aqueous solution containing 5.9 g was added by the double jet method in 37 seconds. Then, after adding 18.6 g of gelatin, 70
The temperature was raised to 0 ° C. and 89 cc of an aqueous silver nitrate solution (silver nitrate 9.8 g) was added over 22 minutes. Here, 7 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 6.5 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added.
While maintaining Ag of 8.5, the mixture was added by the control double jet method over 35 minutes. Next, 15 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Monodispersed pure silver bromide tabular grains having an average projected area diameter of 1.10 μm, a thickness of 0.165 μm and a variation coefficient of diameter of 18.5% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was raised to 40 ° C again, and 30 g of gelatin and 2.3 of phenoxyethanol were used.
Add 5 g and 0.8 g of sodium polystyrene sulfonate as a thickener, and add pH with caustic soda and silver nitrate solution.
It was adjusted to 5.90 and pAg 8.25. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. However, AgI fine particles were added during the chemical sensitization to adjust the silver iodide content to 0.2%. First, 0.043 mg of thiourea dioxide was added and the mixture was held for 22 minutes as it was for reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and sensitizing dye

[0145]

[Chemical 33]

400 mg of was added. Further, 0.83 g of calcium chloride was added. Subsequently, 1.3 mg of sodium thiosulfate, 2.7 mg of selenium compound-1, 2.6 mg of chloroauric acid, and 90 mg of potassium thiocyanate were added.
After 0 minutes, it was cooled to 35 ° C. Thus tabular grains T-1
Was prepared.

Selenium compound-1

[0148]

[Chemical 34]

Preparation of Coating Sample A coating sample was prepared by adding the following chemicals to 1 mol of silver halide of T-1 to prepare a coating solution.・ Gelatin (including Gel in emulsion) 65.6 g ・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Hardener 1 , 2-Bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 230%.

[0150]

[Chemical 35]

The surface protective layer was prepared and prepared so that each component had the following coating amount. Contents coating weight Gelatin 0.966 g / m ² · sodium polyacrylate surface protective layer (average molecular weight 400,000) 0.023 - 4-hydroxy-6-methyl-1,3,3a, 7- tetrazaindene 0 .015

[0152]

[Chemical 36]

Polymethylmethacrylate (average particle size 3.7 μm) 0.087 Proxel (adjusted to pH 7.4 with NaOH) 0.0005 Further, as a selenium sensitizer, the compound 3 of the present invention was used instead of the selenium compound-1. , 8, 10, 16, 21, 23, 25,
The coated samples using Nos. 27, 32, and 34 were prepared. Preparation of Support (1) Preparation of Dye D-1 for Undercoat Layer The following dyes were ball-milled by the method described in JP-A-63-197943.

[0154]

[Chemical 37]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 4
00 ml (2 mm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observing the obtained dye dispersion, the particle size of the crushed dye has a wide range of diameters from 0.05 to 1.15 μm, and the average particle size was 0.37 μm. Further, centrifugation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D-1 was obtained. (2) Preparation of support Corona discharge treatment was performed on a polyethylene terephthalate film having a thickness of 183 μm that was biaxially stretched, and the first undercoat liquid having the following composition was applied so that the coating amount was 5.1 cc / m ^2. It was applied with a wire bar coater and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0156]

[Chemical 38]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc

[0158]

[Chemical Formula 39]

2,4-Dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc distilled water 900.5 cc A second lower layer having the following composition on the first undercoat layer on both sides. The coating layer is coated on each side so that the coating amount is as described below, and 150 ° C on both sides by the wire bar coater method.
It was applied and dried.・ Gelatin 160 mg / m ²・ Dye Dispersion D-1 (26 mg / m ² as a solid dye component)

[0160]

[Chemical 40]

Matting agent Preparation of polymethylmethacrylate 2.5 mg / m ² photographic material having an average particle size of 2.5 μm The above emulsion layer and surface protective layer were coated on both sides of the prepared support by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . Each sample of the photographic material was exposed to light from both sides for 0.05 seconds using an X Ray Orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. to evaluate the sensitivity. The automatic developing machine used in this experiment is a modified automatic developing machine FPM-9000 manufactured by Fuji Photo Film Co., Ltd. The processing steps are shown in Table 9 below. The average processing amount of the photosensitive material per day is about 200 sheets in terms of the size of quarter cut.

[0162]

[Table 9]

The processing solution and its replenishment are as follows.

Development Processing Preparation of Concentrated Solution

<Developer> Parts Agent A Potassium hydroxide 270 g Potassium sulfite 1125 g Sodium carbonate 450 g Boric acid 75 g Diethylene glycol 150 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamino) ethyl-5-mercaptotetrazole 1.5 g Hydroquinone 405 g 4 -Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 30 g Water was added to 4500 ml.

Parts Agent B Tetraethylene glycol 750 g 3-3′-dithiobishydrocinnamic acid 3 g Glacial acetic acid 75 g 5-Nitroindazole 4.5 g 1-Phenyl-3-pyrazolidone 67.5 g Water was added to 1000 ml.

Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 120 g Water was added to obtain 750 ml.

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N-dimethylamino) -ethyl-5 Mercapto tetrazole 15g Tartaric acid 48g Glacial acetic acid 675g Sodium hydroxide 225g Sulfuric acid (36N) 58.5g Aluminum sulphate 150g Water added 6000ml pH 4.68

Preparation of Processing Solution The above concentrated developer solution was filled in the following container for each parts agent. In this container, the partial containers of the parts agents A, B and C are connected together by the container itself.

Also, the above fixing solution concentrate was filled in the same kind of container.

First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was used as a starter in the developing tank.
Was added.

The processing agent-containing container was turned upside down and inserted into the perforating blade of the processing solution stock tank mounted on the side of the developing machine to break the sealing film of the cap and remove each processing agent in the container. The stock tank was filled.

Each of these processing agents was filled in the developing tank and fixing tank of the developing machine at the following ratios by operating the pumps installed in the developing machine.

Also, every time 8 sheets of the photosensitive material were processed in terms of quarter size, the processing agent stock solution and water were mixed at this ratio and replenished in the processing tank of the automatic developing machine.

Developer Part Agent A 60 ml Part Agent B 13.4 ml Part Agent C 10 ml Water 116.6 ml pH 10.50

Fixing solution Concentrating solution 80 ml Water 120 ml pH 4.62

The washing tank was filled with tap water. Photographic sensitivity immediately after coating and 80% relative humidity of 80%
The photographic sensitivity of the selenium compound of the present invention was measured after being stored for 2 days under the atmosphere described above. The selenium compound of the present invention showed a decrease in sensitivity when stored at high temperature and high humidity as compared with the conventionally known selenium compound-1. The favorable result that the amount is small was obtained.

[0178]

The compound of the present invention suppresses the occurrence of fog during selenium sensitization, as compared with the conventionally known compounds.
In addition, it is possible to stably achieve almost the same high sensitivity, and further it is possible to suppress a change in sensitivity when stored under high temperature and high humidity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Fune, 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that at least one of the silver halide emulsion layers contains at least one compound represented by the following general formula (I). General formula (I) In the formula, R ₁ represents NR ₄ (R ₅ ), SR ₆ , SeR ₇ , X, and a hydrogen atom, and R ₂ and R ₃ are aliphatic groups, aromatic groups, heterocyclic groups, OR ₈ , —NR ₉ (R ₁₀ ), SR ₁₁ , SeR ₁₂ ,
X represents a hydrogen atom. R ₄ , R ₅ , R ₉ , and R ₁₀ represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom, and R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ represent an aliphatic group, an aromatic group. Represents a group group, a heterocyclic group, a hydrogen atom or a cation,
X represents a halogen atom. 2. A silver halide photographic light-sensitive material which is selenium-sensitized with at least one compound represented by the following general formula (I). General formula (I) In the formula, R ₁ represents NR ₄ (R ₅ ), SR ₆ , SeR ₇ , X, and a hydrogen atom, and R ₂ and R ₃ are aliphatic groups, aromatic groups, heterocyclic groups, OR ₈ , —NR ₉ (R ₁₀ ), SR ₁₁ , SeR ₁₂ ,
X represents a hydrogen atom. R ₄ , R ₅ , R ₉ , and R ₁₀ represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom, and R ₆ , R ₇ , R ₈ , R ₁₁ and R ₁₂ represent an aliphatic group, an aromatic group. Represents a group group, a heterocyclic group, a hydrogen atom or a cation,
X represents a halogen atom.