JPH0915777A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the silver halide photographic emulsion low in fog and good in storage stability and high in sensitivity and to provide the silver halide photographic sensitive material using this emulsion. CONSTITUTION: The silver halide photographic sensitive material has at least one silver halide emulsion layer on a support and the emulsion contains a compound, having a group absorbable to silver halide and an instable selenium part, embodiable by the general formula: A-(W)n-Z and a thioyanate, or the emulsion having been selenium-sensitized by using this compound of the general formula and containing the thiocyanate. In the formula, A is an atomic group comprising a group absorbable by the silver halide; Z is an atomic group having the instable selenium part; W is a divalent bonding group; and (n) is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material emulsion, and particularly to a halogen using a silver halide photographic emulsion having improved sensitivity, fog, storability, production stability and color sensitization sensitivity. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, there has been a demand for high sensitivity, excellent graininess, gradation and high sharpness of silver halide photographic light-sensitive materials, good storability, and rapid processing with accelerated development progress. It is getting stronger. In particular, there is a strong demand for higher sensitivity with good fog storage while keeping fog low.

The silver halide emulsion used in the silver halide photographic light-sensitive material is usually chemically sensitized with various chemical substances in order to obtain desired sensitivity, gradation and the like. Specific methods include chalcogen sensitization such as sulfur sensitization, selenium sensitization, and tellurium sensitization, precious metal sensitization using a precious metal such as gold, and reduction sensitization using a reducing agent. Used alone or in combination. In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, as well as rapid processing with a rapid development progress, and various improvements of the above sensitization method have been made. . Of the above sensitization methods, selenium sensitization is described in US Pat.
No. 574944, No. 1602592, No. 1623
No. 499, No. 3297446, No. 3297747
No. 3320069, No. 3408196, No. 3408197, No. 3442553, No. 34
No. 20670, No. 3591385, French Patent No. 2093038, No. 2093209, Japanese Patent Publication No. 52
-34491, 52-34492, 53-29
No. 5, 57-22090, JP-A-59-18053.
No. 6, No. 59-185330, No. 59-181337
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246938, British Patent 255,846
No. 861984, No. 4-25832, No. 4-109240, No. 4-147250, and HE.
HESpencer et al., Journal of Photograph Science
ic Science), Volume 31, pp. 158-169 (19
1983) and the like.

However, in general, selenium sensitization has a greater sensitizing effect than the sulfur sensitization generally performed in the art, but fog is large, and softening tends to occur easily. Many of the above-mentioned known patents improve on these drawbacks, but they have only provided inadequate results, and there has been a keen need for fundamental improvements, especially for suppressing fogging. Particularly when sulfur sensitization and selenium sensitization are used together with gold sensitization, a remarkable increase in sensitivity can be obtained, but fog also increases. Compared with gold-sulfur sensitization, gold-selenium sensitization has a particularly large increase in fog, and development of technology to suppress fog generation, especially development of selenium sensitization with less sensitivity change during storage and less fog generation. Has been desired.
In order to meet such a demand, JP-A-6-208186
No. 6, No. 6-208184, No. 6-317867, No. 6-175258, No. 6-43576, No. 4-25.
No. 832, No. 4-109240, No. 4-147250
The group adsorbed on silver halide as suggested in the publication, for example, the unstable selenium compound having a mercapto group surely reduced the occurrence of fog as shown in the examples below, but had a mercapto group. It requires a larger amount of addition for optimum sensitization and is slightly inferior in sensitivity to reach, compared with the conventionally well-known selenium compound. Therefore,
The development of selenium sensitization technology without such defects has been strongly desired. In addition, in the well-known selenium sensitizers, the fog and arrival sensitivity often fluctuate greatly due to the sensitization of the addition amount, and the addition amount slightly changes from the viewpoint of improving the stability and reproducibility of production. Even so, it has been desired to develop a technique in which the change in the photographic characteristics is small.

[0005]

SUMMARY OF THE INVENTION The first object of the present invention is as follows.
Is to provide a highly sensitive silver halide photographic light-sensitive material. A second object of the present invention is to provide a high-sensitivity silver halide photographic emulsion with low fog and good storage stability, and a silver halide photographic light-sensitive material using the same. A third object of the present invention is to provide a silver halide emulsion having low fog, good production stability and high color sensitization sensitivity, and a silver halide photographic light-sensitive material using the same.

[0006]

The above objects of the present invention are:
Achieved by: This has been achieved by a silver halide photographic light-sensitive material characterized by containing a compound having an adsorptive group to silver halide and an unstable selenium moiety, and thiocyanate. More specifically, a silver halide photographic light-sensitive material comprising a silver halide emulsion characterized by being selenium-sensitized with a compound having an adsorptive group to silver halide and an unstable selenium moiety and containing thiocyanate Achieved

More specific examples of the compound having an adsorptive group to silver halide and an unstable selenium moiety used in the present invention include compounds represented by the following general formula (I). General formula (I) A- (W) n-Z In the formula, A is an atomic group containing a group capable of adsorbing to silver halide, Z is an atomic group containing an unstable selenium moiety, and W is a divalent link. In the group, n represents 0 or 1.

Next, the general formula (I) will be described in detail. In the general formula (I), as the atomic group containing a group capable of adsorbing to silver halide represented by A, specifically, an atomic group having a mercapto group (a mercaptotetrazole group, a mercaptotriazole group, a mercaptoimidazole group, Mercaptothiadiazole group, mercaptooxathiazole group, mercaptobenzthiazole group, mercaptobenzoxazole group, mercaptobenzimidazole group, mercaptotetrazaindene group, mercaptopyridyl group,
Mercaptoalkyl group, mercaptophenyl group, etc.), atomic group having thione group (thiazoline-2-thione group, imidazoline-2-thione group, benzimidazoline-2-thione group, benzothiazoline-2-thione group, etc.) , An atom group forming an imino silver (benzotriazole group, tetrazole group, hydroxyazaindene group, benzimidazole group, benztriazole group, etc.). Preferably, it is a group of atoms having a mercapto group or a thione group.

In the general formula (I), the atom group containing an unstable selenium moiety represented by Z includes (1) selenoureas (eg, N, N-dimethylselenourea, selenourea, N-acetyl-N, N ', N'-trimethylselenourea, N-trifluoroacetyl-N,
N ', N'-trimethylselenourea, etc.), (2) selenoamides (eg, N, N-dimethylselenobenzamide, N, N-diethylselenobenzamide, etc.),
(3) phosphine selenides (for example, triphenylphosphine selenide, diphenyl (pentafluorophenyl) phosphine selenide, tris (m-phenylophenyl) phosphine selenide, etc.), (4) selenophosphates (tri-p-tolyl) Selenophosphate, selenophosphoric acid o, o, o-tris (hydroxyethyl) ester, etc.), (5) selenoesters (for example, p-methoxyselenobenzoic acid o-isopropyl ester, selenobenzoic acid Se- ( 3'-oxobutyl) ester, p-methoxyselenobenzoic acid Se- (3'-oxocyclohexyl) ester), (6) diacyl selenides (for example, bis (2,6-dimethoxybenzoyl) selenide), ( ) Bis (alkoxycarbonyl) selenides (eg, bis (n-butoxycarbonyl) selenide, bis (benzyloxycarbonyl) selenide, etc.), (8) Dicarbamoyl selenides (eg, bis (N, N-dimethylcarbamoyl)) Selenide), (9) triselenane (for example, 2,4,6-tris (p-methoxyphenyl) triselenane),
(10) selenoketones (for example, 4,4'-methoxyselenobenzophenone and the like), (11) diselenides,
Polyselenides (12) Selenocarboxylic acids (13) Isoselenocyanates (p-tolyl isoselenocyanate, cyclohexyl isoselenocyanate, etc.), (14) Selenourethanes, Selenocarbonic acid esters, Selenohitrazides, (15) ) Selenols, and the like. Preferably, selenoureas, selenoamides, phosphine selenides, bis (alkoxycarbonyl) selenides, triselenanes, isoselenocyanates, selenourethanes, selenocarbonates, selenohydrazides, selenoesters are preferred. Can be More preferred are selenoureas, selenamides, phosphine selenides, bis (alkoxycarbonyl) selenides, and selenoesters. General formula (I)
Wherein the divalent linking group represented by W is a carbon atom, a hydrogen atom,
Represents a divalent linking group composed of an oxygen atom, a nitrogen atom, and a sulfur atom, specifically, an alkylene group having 1 to 20 carbon atoms (methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, etc. ), An arylene group having 6 to 20 carbon atoms (phenylene group, naphthylene group, etc.), -C
ONR _1- , -SO ₂ NR _2- , -O-, -S-, -N
_{R 3 -, - NR 4 CO} -, - NR 5 SO 2 -, - NR 6
_{CONR 7 -, - COO -,} - OCO- , and the like. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ or R ₇ represents a hydrogen atom, an aliphatic group or an aromatic group.

In the general formula (I), R ₁ , R ₂ ,
_{R 3, R 4, R 5} , the aliphatic group represented by R ₆ or R _7, is preferably straight-chain, especially 1 to 20 carbon atoms be of 1 to 30 carbon atoms, branched or cyclic An alkyl group, an alkenyl group, an alkynyl group, and an aralkyl group. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include a methyl group, an ethyl group, an isopropyl group,
t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group,
Examples thereof include a cyclohexyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group, a propargyl group, a 3-pentynyl group and a benzyl group.

In the general formula (I), R ₁ , R ₂ ,
The aromatic group represented by R ₃ , R ₄ , R ₅ , R ₆ , or R ₇ is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed ring having 6 to 20 carbon atoms. An aryl group,
For example, a phenyl group, a naphthyl group, etc. The above groups may be combined with each other to form a divalent linking group.

Specific examples of the compound of the present invention are shown below, but the compound of the present invention is not limited thereto.

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

As the thiocyanate used in the present invention, a water-soluble thiocyanate is used, and examples thereof include potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate.

The thiocyanate used in the present invention may be added at any time during the preparation of silver halide emulsion, for example, during the formation of silver halide grains, during the washing with water, before chemical sensitization or before the end of chemical sensitization. . The compound of the general formula (I) may coexist when sensitizing with selenium.

The amount of the selenium compound of the general formula (I) used in the present invention varies depending on the silver halide grains used and the chemical sensitization conditions, but is 10 ^-8 to 10 ^-2 per mol of silver halide. A molar amount, preferably about 10 ⁻⁷ to 10 ⁻³ mol, can be used.

The amount of thiocyanate used in the present invention varies depending on the silver halide grains used, the timing of use, the chemical sensitization conditions, etc., but is 10 ^-5 to 10 ^-1 mol per mol of silver halide. , Preferably 10 ^{−4 to} 5 × 10 ⁻²
Molar amounts can be used.

The conditions for sensitizing selenium in the present invention are not particularly limited, but pAg is 6 to 11, preferably 7 to 10, and pH is 4 to 10, preferably 5.
~ 8, as a temperature 40 ~ 95 ℃, preferably 45 ℃
８５85 ° C.

Although the above-mentioned known patents describing unstable selenium compounds describe that thiocyanate may be used in the chemical sensitization, the general formula of the present invention ( There was no specific disclosure of a combination of a selenium compound represented by I) and a thiocyanate. As shown in the examples below, the effect of using a thiocyanate in combination with the selenium compound of the present invention is far greater than the effect of using a thiocyanate in combination with a conventionally well-known selenium compound,
It was unexpected.

In addition to the silver halide photographic emulsion of the present invention,
Sulfur sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization are preferably used alone or in combination. For sulfur sensitization, unstable sulfur compounds are used, and P.
Grafkides, Chimie et Physique Photographique (Pau
l Momtel, 1987, 5th edition), ResearchDiscl
Unstable sulfur compounds described in Osure magazine 307, 307105, etc. can be used. Specifically, thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-
N '-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (for example, thioacetamide), rhodanines (for example, diethylrhodanine, 5-benzylidene-N-ethylrhodamine) , Phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins,
Known sulfur compounds such as 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (for example, dimorpholine disulfide, cystine, lenthionine), polythionate, active gelatin and the like can also be used.

Further, in addition to the compound (I) of the present invention, a conventional selenium compound may be further used as long as it does not interfere. As the unstable selenium compound, Japanese Patent Publication No.
89, 44-15748, and JP-A-4-25832.
No. 4-109340, No. 4-271341, No. 5-40324, No. 5-11385, Japanese Patent Application No. 4-2.
No. 02415, No. 4-330495, No. 4-3330.
No. 30, No. 5-4203, No. 5-4204, No. 5-
No. 106977, No. 5-236538, No. 5-241.
The selenium compounds described in No. 642 and No. 5-286916 can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenamides (eg, selenamide, N, N).
-Diethylphenyl selenamide), phosphine selenides (eg, triphenylphosphine selenide,
Pentafluorophenyl-diphenylphosphine selenide), selenophosphates (eg tri-p-
Trilylselenophosphate, tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters, diacylselenides and the like may be used. Furthermore, Japanese Patent Publication No. 46-4553
No. 52-34492 and the like, non-unstable selenium compounds such as selenious acid and potassium selenocyanate,
Selenazoles and selenides can also be used.

In tellurium sensitization, an unstable tellurium compound is used, and JP-A-4-224595 and JP-A-4-2713 are used.
No. 41, 4-333430 and 5-303157
Japanese Patent Application No. 4-185004 and No. 4-330495.
No. 4, No. 4-333030, No. 5-4203, No. 5-
No. 4204, No. 5-106977, No. 5-28691.
Unstable tellurium compounds described in No. 6 can be used. Specifically, phosphine tellurides (for example, butyl-diisopropylphosphine telluride,
Tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (for example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride Bis (N-phenyl-N-methylcarbamoyl) telluride,
Bis (N-phenyl-N-benzylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), telluroureas (for example, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea) telluroamides, Telluroesters may be used.

In sensitizing precious metals, P. Grafkides,
Chimie et Physique Photographique (Paul Momtel, 1987, 5th edition), Research Disclosure magazine 3
07, 307105, etc., gold, platinum,
Noble metal salts such as paradium and iridium can be used, and gold sensitization is particularly preferable. In particular,
In addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide, US Pat. Nos. 2,642,361, 5,049,484, and 50,
No. 49485, No. 5169751, No. 5252455
The gold compounds described in Japanese Patent No. 6918857, etc. can also be used.

In reduction sensitization, P. Grafkides, Ch
imie et Physique Photographique (published by Paul Momtel,
1987, 5th edition), Research Disclosure 307
The reducing compounds described in Vol. 307105 and Japanese Patent Application No. 7-78685 can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (eg, dimethylamineborane), hydrazine compound (eg, hydrazine, p-
Trilyhydrazine), polyamine compounds (eg, diethylenetriamine, triethylenetetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sodium sulfite, aldehyde compounds,
Hydrogen gas or the like may be used. Further, reduction sensitization may be performed in an atmosphere of high pH or excess silver ions (so-called silver ripening). In particular, it is preferable to carry out reduction sensitization during the formation of silver halide grains.

Of these chemical sensitizations, a combination with gold sensitization is preferable.

Further, in the present invention, for the chemical sensitization of silver halide, other silver halide solvent may be further used in addition to thiocyanate. Specifically, thioether compounds (see, for example, US Pat.
2711157, Japanese Examined Patent Publication No. 58-30571, JP-A-6
Compounds described in 0-136736, particularly 3,6-dithia-1,8-octanediol, etc., tetra-substituted thiourea compounds (for example, compounds described in JP-B-59-11892, U.S. Pat. No. 4,221,863, In particular, tetramethylthiourea), a thione compound described in JP-B-60-1134, a mercapto compound described in JP-B-63-29727, a mesoionic compound described in JP-A-60-163042, and U.S. Pat. The selenoether compounds described in JP-A No. 2-118566, and the terether compounds and sulfites described in JP-A-2-118566. Especially,
Among these, thioether compounds, tetra-substituted thiourea compounds and thione compounds can be preferably used. The amount used is 10 ^-5 to 10 ^-2 per mol of silver halide.
It is about a mole.

Next, the silver halide emulsion of the present invention and a silver halide photographic light-sensitive material (sometimes referred to simply as a light-sensitive material) using the same will be described. The above silver halide photographic light-sensitive material has a silver halide emulsion layer on a support. Silver halide emulsion used in the present invention,
Silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride are preferred. Silver halide grains used in the present invention,
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. Although a mixture of particles of various crystal forms can be used, it is preferable to use a regular crystal form.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer or may be composed of a uniform phase. A 2-structured particle having different iodine compositions between the inside of the particle and the surface layer (in particular, the iodine content inside is larger) is also preferable. Further, it may be a grain in which a latent image is mainly formed on the surface (for example, a negative emulsion), or a grain mainly formed inside the grain (for example, an internal latent image type emulsion, a direct inversion type emulsion which has been fogged in advance). ) May be sufficient. Preferably, the particles are such that the latent image is mainly formed on the surface. Further, grains containing dislocation lines are preferable. The silver halide emulsion used in the present invention contains tabular silver halide grains having an aspect ratio of 3 or more, preferably tabular silver halide grains having an average aspect ratio of 3 or more and less than 8.
Preferably, 60% or more of the total projected area is occupied by such tabular silver halide grains. The tabular grains preferably have a diameter of 0.15 to 5.0 μm. The thickness of the tabular grains is preferably 0.05 to 1.0 μm. The average aspect ratio is at least 100
It is calculated as the arithmetic mean of the aspect ratios of individual silver halide grains. It can also be determined as the ratio of the average diameter to the average thickness of the particles.

In the case of normal crystals or spherical or three-dimensional particles, the diameter is 0.05 μm to 3 μm, preferably 0.08 μm to 2 μm, and the coefficient of variation is 20% or less,
A monodispersed emulsion of 15% or less is more preferable. The principal plane of tabular grains may be the (111) plane or the (100) plane.

Further preferable results can be obtained by using monodisperse tabular grains. The structure and manufacturing method of the monodisperse tabular grains are described in, for example, JP-A No. 63-151618. Briefly describing the shape, 70% or more of the total projected area of silver halide grains is the minimum. Occupied by tabular silver halide having a hexagonal shape in which the ratio of the length of the side having the maximum length to the length of the side having the length is 2 or less and having two parallel parallel surfaces as outer surfaces. Furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains (the variation of the grain size represented by the diameter of the projected area in terms of circle (standard deviation) divided by the average grain size) Has a monodispersity of 20% or less.

Further, the emulsion of the present invention preferably has dislocation lines. The dislocations of tabular grains are, for example, JF Hamil
ton, Phot. Sci. Eng., 11, 57, (1967)
T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 21
3, (1972), and can be observed by a direct method using a transmission electron microscope at low temperature.

When forming the silver halide grains,
As a silver halide solvent for controlling the growth of grains, for example, ammonia, rodancali, rhodammone, thioether compounds (for example, US Pat. No. 3271).
No. 157, No. 3574628, No. 3704130.
No. 4,297,439, No. 4,276,374),
A thione compound (for example, JP-A-53-144319, JP-A-53-82408, JP-A-55-77737) and an amine compound (for example, JP-A-54-100717) can be used.

In the process of silver halide grain formation or physical ripening, ruthenium salt, zinc salt, chromium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may be present together. Particularly, iridium salt, iron salt and rhodium salt are preferable. As the binder or protective colloid that can be used in the emulsion layer and intermediate layer of the photographic light-sensitive material, it is advantageous to use gelatin,
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, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal,
Various synthetic hydrophilic polymeric substances such as poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole homopolymer or copolymer can be used.

The tabular grains of the present invention are described by Cleve in "Theory and Practice of Photography" (Cleve, Photography Theory and Practice).
(1930)), p. 131; Gatov, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,43
It can be prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157. In addition to general-purpose lime-processed gelatin, acid gelatin and the Japan Society for Science and Photography (Bul)
L. Soc. Phot. Japan), No. 16, p. 30 (196
The enzyme-treated gelatin as described in 6) may be used, or a hydrolyzate of gelatin may be used.

The photographic light-sensitive material may contain an inorganic or organic hardener in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. For example, chrome salt,
Specific examples thereof include aldehyde salts (eg formaldehyde, glyoxal, glutaraldehyde) and N-methylol compounds (eg dimethylolurea). Active halogen compounds (eg 2,4-dichloro-6)
-Hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (eg 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ) An ether or a vinyl polymer having a vinyl sulfonyl group in the side chain) is preferable because it rapidly cures a hydrophilic colloid such as gelatin and gives stable photographic characteristics. N-carbamoylpyridinium salts (eg (1-morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (eg 1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfonate) also cure Good early.

The silver halide photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or 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 are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes.
That is, the pyrroline nucleus includes an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, Benzimidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may have a substituent on a carbon atom.

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

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic nucleus group (for example, US Pat. Nos. 2,933,390 and 36)
No. 35721), formaldehyde condensates of aromatic organic acids (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. U.S. Pat. Nos. 3,615,613 and 361
The combinations described in 5641, 3617295 and 3635721 are particularly useful.

The silver halide photographic emulsion used in the present invention 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 (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadlithione; azaindenes; Triazaindenes, tetraazaindenes (especially 4-hydroxy-6
-Methyl (1,3,3a, 7) tetraazaindene),
Pentaazaindenes; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amides can be added.

The photographic light-sensitive material may contain one or more surfactants for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, hardening, sensitization). May be included.

The photographic light-sensitive material is used as a filter dye.
Alternatively, a water-soluble dye may be contained in the hydrophilic colloid layer for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used.In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The photographic light-sensitive material has at least 2 on the support.
It can be constructed as a multilayer multicolor photographic material having two different spectral sensitivities. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red sensitivity, green sensitivity and blue sensitivity, blue sensitivity, green sensitivity and red sensitivity or blue sensitivity, red sensitivity and green sensitivity. In addition, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the reaching sensitivity, or a three-layer constitution may be used to further improve the graininess.
Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer of fine grain silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity. Additives used in the silver halide emulsion used in the present invention are Research Disclosure No. 17643 and No. 17643.
18716 and No. 307105, and the corresponding parts are summarized in the table below.

Types of additives RD17643 RD18716 RD307105 [December 1978] [November 1979] [November 1989] 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Brightener Page 24 Page 647 Right column Page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. 7. Stain inhibitor 25 pages, right column, 650 pages, left to right column, 872 pages Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener page 26 page 651 left column 874 to 875 page 10. Binder page 26 page 651 page left column 873 to 874 page 11. plasticizer and lubricant page 27 page 650 right column page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Antistatic agent, page 27, page 650, right column, pages 876 to 877 14. Matting agents pp. 878-879 For other techniques and inorganic / organic materials that can be used in the photographic light-sensitive material of the present invention, see European Patent No. 43.
No. 6,938A2, and in the patents cited below. 1. 1. Layer structure: page 146, line 34 to page 147, line 25 2. Yellow coupler: page 137, line 35 to page 146, line 33, page 149, lines 21 to 23 3. Magenta coupler: page 149, lines 24 to 28; EP 421,453A1, page 3, line 5 to page 25, line 55 4. Cyan coupler: page 149, lines 29 to 33; EP 432,804 A2, page 3, line 28 to page 40, line 2 5. Polymer coupler: page 149, lines 34 to 38; EP 435, 334A2, page 113, line 39 to page 123, line 37. 6. Colored coupler: page 53, line 42 to page 137, line 34, page 149, line 39 to line 45 Other functional couplers: page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3; page 3, line 1 of EP 435,334 A2 ~ From page 29, line 508. 8. Antiseptic / antifungal agent: page 150, lines 25-28 Formalin scavenger: page 149, lines 15 to 17 10. Other additives: page 153, lines 38 to 47; European Patent 421,4 53A1, page 75, lines 21 to 84. Line 56, page 27, line 40 to page 37, line 40 11. Dispersion method: Page 150, line 4 to line 24 12. Support: Page 150, line 32 to line 34 13. Membrane Thickness / Film Properties: Page 150, Lines 35 to 49 14. Color development process: Page 150, Lines 50 to 151, Line 47 15. Desilvering process: Page 151, Line 48 to Page 152 53 Line 16. Automatic processor: Page 152, Line 54-Page 153, Line 2 17. Washing and stabilization process: page 153, lines 3 to 37

(1) A silver halide photographic emulsion characterized by being selenium-sensitized with a selenium compound of the general formula (I) having an adsorptive group to silver halide and an unstable selenium moiety and containing a thiocyanate salt. . (2) Thiocyanate is preferably 10 × ^-4 mol / mol Ag or more, particularly preferably 5 × 10 ^-4 mol / mol Ag.
A silver halide emulsion characterized by being selenium-sensitized with a selenium compound represented by formula (I) in the presence above. (3) In the general formula (I), the adsorptive group is a mercapto group,
A selenium compound having a thione group or a group that produces imino silver. (4) The compound in which the adsorptive group in the general formula (I) is a mercapto group or a thione group. (5) In formula (I), the atom group containing an unstable selenium moiety is selenoureas, selenoamides, phosphine selenides, bis (alkoxycarbonyl) selenides,
Triselenane, isoselenocyanate, selenourethane, selenocarbonate, selenohydrazide,
It must be a compound of selenoesters. (6) In general formula (I), the atom group containing an unstable selenium moiety is selenoureas, selenoamides, phosphine selenides, bis (alkoxycarbonyl) selenides,
It must be a compound of selenoesters. (7) The thiocyanate is potassium thiocyanate, sodium thiocyanate, or ammonium thiocyanate. (8) The silver halide emulsion of the present invention is further subjected to reduction sensitization, and preferably reduction sensitization is performed during the formation of silver halide grains. (9) The silver halide emulsion of the present invention is further subjected to sulfur or tellurium chalcogen sensitization. (10) The silver halide emulsion of the present invention has been subjected to gold sensitization. (11) The silver halide emulsion of the present invention is chemically sensitized by combining chalcogen sensitization of sulfur or tellurium and gold sensitization. (12) The silver halide photographic emulsion of the present invention is spectrally sensitized by adding a methine dye. (13) The methine dye of (12) is a cyanine dye. (14) The silver halide emulsion of the present invention is silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, or silver chloride. (15) The silver halide emulsion of the present invention is a normal crystal or tabular grain. (16) The silver halide emulsion grain of the present invention contains a dislocation line. (17) A silver halide photographic light-sensitive material containing at least one silver halide emulsion described in (1) to (16). Specific examples of the present invention will be given below, but the present invention is not limited to the following examples unless the gist of the present invention is exceeded.

[0048]

【Example】

Example 1 While stirring a gelatin aqueous solution containing potassium bromide and ammonia kept at 60 ° C., an aqueous silver nitrate solution and an aqueous potassium bromide solution were added by a double jet method while keeping the silver potential at +10 mV with respect to a saturated calomel electrode. . After forming the particles, desalting and washing were carried out by a conventional flocculation method, gelatin and water were added to adjust pH to 6.0 and pAg to 8.8.
The obtained silver bromide emulsion had a grain diameter of 0.8 μm, (11
It is a monodisperse tetradecahedral emulsion having a 1) face / (100) face ratio of 65/35 and a variation coefficient of grain diameter of 10%. This emulsion was subdivided, heated to 60 ° C., potassium thiocyanate was added as shown in Table 1, and 2 minutes later, a selenium compound was added and ripened for 60 minutes. Then, a magenta coupler; 3- {3- [2- (2,4-di-tert-amylphenoxy) butylamino] benzoylamino} -1-
(2,4,6-Trichlorophenyl) pyrazolone-5-
On, oil; tricresyl phosphate, stabilizer;
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, coating aid; sodium dodecylbenzene sulfonate, hardener; 1,2-bis (vinylsulfonylacetylamino) ethane, preservative; Phenoxyethanol was added and coated by coextrusion onto a triacetyl cellulose film support having a subbing layer with a gelatin protective layer containing methyl polymethacrylate particles. These samples were exposed under a light wedge (1 second) and subjected to the following development processing. (Processing method) Process processing time processing temperature color development 2 minutes 15 seconds 38 ° C bleaching 6 minutes 30 seconds 38 ° C water washing 2 minutes 10 seconds 24 ° C settling 4 minutes 20 seconds 38 ° C water washing (1) 1 minute 05 seconds 24 ℃ Wash with water (2) 1 minute 00 seconds 24 ℃ Stability 1 minute 05 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃

Next, the composition of the treatment liquid is shown. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 water was added to 1.0 liter pH 10.05

(Bleaching Solution) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6 Add 0.5 ml water 1.0 liter pH 6.0

(Fixing Solution) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170.0 ml 1.0 liter with addition of water pH 6.7

(Stabilizing Solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether 0.3 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water In addition, the concentration of the treated sample of 1.0 liter pH 5.0-8.0 was measured with a green filter. Table 1 shows the obtained photographic performance results. The relative sensitivity is represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog value + 0.2.

[0053]

[Table 1]

[0054]

[Table 2]

As is clear from Table 1, the selenium compound of the present invention having an adsorptive group produces less fog than the comparative compounds 1 and 2 which do not have an adsorptive group. The reach sensitivity will be slightly lower. However,
When potassium thiocyanate was added to this, the sensitization was remarkably sensitized, the addition amount was as small as that of the comparative compound, and the fog was also low. In contrast, comparative compounds 1 and 2
In addition, even if potassium thiocyanate was used in combination, the sensitization due to it was slight and the addition amount was not reduced, and the effect of potassium thiocyanate on the selenium compound of the present invention was very unexpected. Also, samples 1 to 6 and 13 to 2
As can be seen from 0, the fog and the sensitivity of Comparative Compounds 1 and 2 greatly fluctuate with respect to the change of the addition amount, and even if potassium thiocyanate is used in combination, it is not improved. On the other hand, the selenium compound of the present invention has a small variation even when used alone, is sensitized by the combined use of potassium thiocyanate, and has less fogging and variation in sensitivity due to a change in the addition amount, and has excellent emulsion production stability. It became a thing.

Example 2 Silver bromide tabular grains having a thickness of 0.1 μm and an equivalent circle diameter of 0.7 μm were prepared as seed crystals. Seed crystals containing 6 g of Ag 1.0
Dissolve in liters of distilled water, pAg 8.2, pH 5
The temperature was adjusted to 70 ° C., the temperature was kept at 70 ° C., and the mixture was vigorously stirred. continue,
Particle formation was performed by the following procedure. AgNO ₃ (166
g) Aqueous solution and KBr aqueous solution were added while keeping pAg at 8.4. At this time, the reduction sensitizer thiourea dioxide (1.5 mg) was also added. The temperature was lowered to 55 ° C and KI (8g)
The aqueous solution was added at a constant flow rate. An aqueous solution of AgNO ₃ (38 g) and an aqueous solution of KBr were added while keeping pAg at 8.9, and finally sodium benzenethiosulfonate (42 m
g) was added.

The mixture was cooled to 35 ° C., washed with water by a conventional flocculation method, added with 50 g of gelatin, pH 5.9, p.
Prepared to Ag 8.5. The resulting emulsion contained 81% of the total projected area of tabular grains having an average equivalent spherical diameter of 0.85 μm and an aspect ratio of 3 or more, and many dislocation lines were observed by an electron microscope. This emulsion was divided into small portions, each of which was heated to 56 ° C, and then anhydro-5-chloro-5'-phenyl-
9-Ethyl-3,3′-di (3-sulfopropyl) benzoxacarbocyanine hydroxide sodium salt was added, and 10 minutes later, chloroauric acid (4.2 × 10 ⁻⁶ mol / mol Ag) and sulfur were added. Sensitizer Hypo (9 × 10 ^-6 mol /
Mol Ag), and then potassium thiocyanate and a selenium compound shown in Table 2 were sequentially added at intervals of 2 minutes to give 1/100.
It was aged so that the sensitivity of second exposure was optimal.

Then, the magenta coupler; 3- {3-
[2- (2,4-di-tert-amylphenoxy) butylamino] benzoylamino} -1- (2,4,6-
Trichlorophenyl) pyrazolone-5-one oil; tricresyl phosphate stabilizer; 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene antifoggant; 1- (m-sulfophenyl) -5-mercaptotetrazole monosodium salt and 1- (p-carboxyphenyl) -5-mercaptotetrazole coating aid Agent; sodium dodecylbenzene sulfonate Hardener; 1,2-
A bis (vinylsulfonylacetylamino) ethane preservative; phenoxyethanol was added and coated by coextrusion onto a triacetyl cellulose film support having a subbing layer with a gelatin protective layer containing polymethylmethacrylate microparticles.

These samples were exposed for sensitometry (1/100 second) through a yellow filter and subjected to the same color development process as in Example 1.

The density of the treated sample was measured with a green filter. Table 2 shows the obtained photographic performance results. The relative sensitivity was represented by the relative value of the reciprocal of the exposure amount required to obtain the optical density of (fog value + maximum density / 2), and the value of Sample 31 was set to 100.

[0061]

[Table 3]

As is clear from Table 2, when the selenium compound of the present invention was used in combination with potassium thiocyanate, the sensitivity was remarkably increased and low fog and high spectral sensitivity could be obtained. Further, the fog and the change in the spectral sensitivity when stored under high temperature and high humidity were improved as compared with the comparative compound.

Example 3 3.3 g of sodium chloride and gelatin 2 kept at 55 ° C.
To 800 ml of an aqueous solution of pH 4.5 in which 5 g was dissolved, an aqueous solution of silver nitrate (170 g of AgNO ₃ and 480 ml of water) and an aqueous solution of sodium chloride containing 0.3 mg of potassium hexachloride iridium salt (59 g of NaCl and 480 m of water were added).
l) was added simultaneously. One minute before the end of the addition, an aqueous solution containing 0.1 g of potassium thiocyanate and 1.2 g of KBr was added. The resulting emulsion has a grain size of 0.45 μm in side length.
It was a cubic, monodisperse silver chloride emulsion of m. afterwards,
After washing with water and desalting by a normal flocculation method using a polymer flocculant, 76 g of gelatin and water were added to the mixture to give 4
The pH was adjusted to 6.2 and the pAg was adjusted to 7.0 at 0 ° C. The emulsion was divided into small portions, the temperature was raised to 55 ° C., the selenium compounds shown in Table 3 were added, and the mixture was ripened for 40 minutes. Then, gelatin, water, and stabilizers; 4-hydroxy-6-methyl, 1,3,3a,
7-Tetrazaindene antifoggant; 1- [3- (3-methylureido) phenyl] -5-mercaptotetrazole Coating aid; Sodium dodecylbenzene sulfonate Hardener; 2,4-Dichloro-6-hydroxy- S-triazine sodium salt was sequentially added and coated on a paper support laminated on both sides with polyethylene together with a gelatin protective layer to obtain a sample.

The sample was exposed under a light wedge (1/10 seconds), subjected to black and white development treatment at 20 ° C. for 5 minutes with the following developer, and then stopped, fixed, washed with water and dried by a conventional method, and the density was measured. The results shown in Table 3 were obtained. However, the relative sensitivity is the fog value +
It was expressed by the relative value of the reciprocal of the exposure amount required to give a density of 0.5, and that of Sample 41 was set to 100. The composition of the treatment liquid is shown below. Metol 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g KBr 1.0 g Water was added to 1.0 liter pH (prepared) 9.6

[0065]

[Table 4]

As is clear from Table 3, even in the high silver chloride emulsion using potassium thiocyanate during grain formation,
The selenium compound of the present invention has remarkably low fog and the same or higher sensitivity was obtained. This result also adds a coupler,
The same was true when color development was performed.

Example 4 Em-32 obtained with the emulsion used in Sample 17 of Example 1
Sample 6 of Example 3 of JP-A-6-258788
Using the same as the fifth layer of the light-sensitive material of (Sample No. 101), the same treatment as in the same example was performed and good performance was obtained.

Example 5 Em-32 obtained with the emulsion used in sample 34 of example 2.
Was used as an emulsion of the light-sensitive material-X of Example 1 of JP-A-6-273860, combined with the screen B, and processed as in the same example to obtain good performance.

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

[Procedure amendment]

[Submission date] July 15, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

Example 5 Em-32 obtained with the emulsion used in sample 34 of example 2.
Was used as an emulsion of the light-sensitive material-X of Example 1 of JP-A-6-273866, combined with the screen B, and processed as in the same example to obtain good performance.

Claims (4)

[Claims] 1. A support comprising at least one silver halide emulsion layer on a support, containing a compound having an adsorbing group for silver halide and an unstable selenium moiety, and thiocyanate. A silver halide photographic light-sensitive material. 2. The compound having an adsorptive group to silver halide and an unstable selenium moiety described in claim 1 is a compound represented by the following general formula (I). The silver halide photographic light-sensitive material described in. General formula (I) A- (W) n-Z In the formula, A is an atomic group containing a group capable of adsorbing to silver halide, Z is an atomic group containing an unstable selenium moiety, and W is a divalent link. In the group, n represents 0 or 1. 3. A silver halide photographic emulsion characterized by being selenium-sensitized with a compound having an adsorptive group to silver halide and an unstable selenium moiety and containing a thiocyanate. 4. The compound having an adsorptive group to silver halide and an unstable selenium moiety described in claim 3 is a compound represented by the following general formula (I). The silver halide photographic emulsion according to 1. General formula (I) A- (W) n-Z In the formula, A is an atomic group containing a group capable of adsorbing to silver halide, Z is an atomic group containing an unstable selenium moiety, and W is a divalent link. In the group, n represents 0 or 1.