JPH0651415A - Production of silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To provide a production method of silver halide photographic emulsion having high sensitivity for high illuminance and little dependence on exposure illuminance. CONSTITUTION:The silver halide photographic emulsion is produced by using such a compd. containing at least one kind of metal complex ion expressed by general formula described below as the whole or a part of the structure. General formula: [MXnY4-n]<m->, wherein M is molybdenum, tungsten, rhenium, vanadium, niobium, or tantalum, X and Y are oxygen, sulfur, selenium, or tellurium, (n) is 0-4, and m is 1-3. However, at least one of X and Y is sulfur, selenium or tellurium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide photographic emulsion having high illuminance sensitivity.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material, chemical sensitization is performed by using various chemical sensitizers to obtain high-sensitivity and high-quality images. However, it is necessary to improve the characteristics of silver halide grains. For example, it is desired to further enhance the high-sensitivity image quality by incorporating the metal complex into the particles or by adding the metal complex after the formation of the particles and fixing the metal complex on the surface.

Techniques for introducing or introducing a metal complex at any stage immediately before emulsion preparation and coating are described in US Pat.
No. 060. The metal complex at this time is represented by the general formula R ₂ MX ₆ in which R represents hydrogen, an alkali metal or an ammonium group, and M is a transition metal of the platinum group excluding osmium, for example, platinum, palladium, iridium, rhodium or ruthenium. And X represents a halogen atom, for example chlorine or bromine. These metal complexes are water-soluble, and when they are introduced, they are effective as a fog-preventing and stabilizing agent.
It is shown that sensitization can be achieved when the hexacoordinated metal complex of is added.

[0004] Many reported examples of hexacoordinated metal complexes having a halide ion as a ligand have been known thereafter. Other ligands of halide ions such as nitrosyl, thionitrosyl, carbonyl, cyanide ion, thiocyanide ion, selenocyanide ion, tellurocyanide ion, azide ion, oxide ion, sulfite ion and nitrite ion in recent years. For (including nitrito), it has been reported to introduce a hexacoordinated metal complex into particles. For example, JP-A Nos. 2-20,854 and 2-20,85
No. 3, No. 2-20,852, No. 2-20,855, No. 3-118,535, No. 3-118,535, No. 4
-97,337 and the like.

Further, in US Pat. No. 4,997,751 and JP-A-3-15,040, a metal complex of iridium is used as a chemical sensitizer after grain formation and is fixed near the grain surface to obtain low illuminance. The failure is being improved.

However, the use of these metal complexes in the particles or after the formation of the particles was effective in improving the low illuminance failure and increasing the gradation, but was particularly disadvantageous in terms of high illuminance failure and sensitivity. . Further, in these patents, there is no description about sulfide ion, and the metal complexes used are all those having a hexacoordinate octahedral structure, and those having a tetracoordinate tetrahedral structure are described. Not not.

In addition to the above, chemical sensitization is usually performed using various chemical substances containing no heavy metal in order to obtain desired sensitivity and gradation. Typical methods include chalcogenide sensitization of sulfur, selenium, tellurium and the like. The most basic of these is the sulfur sensitization method using a so-called unstable sulfur compound that can react with silver ions to form silver sulfide, and specifically, P. Grafkide
Chisie et Physique Photographique (Paul Mont
published by el, 1987, 5th edition), edited by TH James, The
Theory of the Photographic Process (Macmillan, 1977, 4th edition), H. Frieser, Die Grundl
agender Photographischen Prozess mitSilver-halogen
iden (Akademische Verlagsgeselbshaft, 1968)
Etc.

In the selenium sensitization, known unstable selenium compounds, specifically, colloidal metal selenium, JP-B-44-15748 and JP-B-43-1348 are used.
No. 9, Japanese Patent Application Nos. 2-130976 and 2-229300.
No. 2, No. 2-272879, No. 3-53693, No. 3
The compounds described in No. 82929 and the like are shown.

For tellurium sensitizers, US Pat.
623, 499, 3,320,069, 3,7
72,031, British Patent No. 235,211 and 1,
121, 496, 1, 2, 295, 462, 1, 3
96,696, Canadian Patent No. 800,958, Journal of Chemical Society Chemicals.
Communication (J. Chem. Soc., Chem. Commun.)
635 (1980), ibid. 1102 (1979), ibid. 64
5 (1979), Journal of Chemical Society Parkinson Transactions (J. Chem.
Soc., Perkin. Trans.) 1, 2191 (1980), Japanese Patent Application Nos. 2-333819 and 3-131598, and the like are known.

These chalcogenide sensitizations have drawbacks such as a large change in sensitivity gradation due to exposure illuminance under environmental conditions during chemical sensitization, and particularly low high illuminance sensitivity.

Using a compound containing a metal complex ion such as molybdenum or tungsten similar to the present invention is disclosed in British Patent No. 385,545 and US Pat. No. 1,982,98.
No. 7, but this is only for silver molybdate or silver tungstate, not for use with those containing sulfur, selenium, tellurium.

[0012]

From the above, it has been desired to improve the characteristics of silver halide grains in order to provide a silver halide emulsion having a high image quality with high sensitivity. An object of the present invention is to provide a method for producing a silver halide photographic emulsion having high sensitivity to high illuminance and less dependency on exposure illuminance.

[0013]

[Means for Solving the Problems] The above objects have been achieved by the following. That is, it was achieved by a method for producing a silver halide photographic emulsion, which is characterized in that it is produced using a compound containing at least one metal complex ion represented by the following general formula (I). General formula (I) [MX _n Y _4-n ] ^{m-In the} formula, M represents molybdenum, tungsten, rhenium, vanadium, niobium or tantalum. X and Y are oxygen,
Represents sulfur, selenium or tellurium, n is 0 to 4, m
Represents a number from 1 to 3. However, at least one of X and Y represents sulfur, selenium, or tellurium.

Of the metal complex ions represented by the general formula (I), the metal is preferably molybdenum and tungsten. Since the metal complex ion represented by the general formula (I) contains a chalcogen atom having a coordinating ability, the metal complex ion itself can serve as a ligand for another metal ion. Since the structure of the metal complex ion represented by the general formula (I) is important in the present invention, it may be a single structure or a partial structure of a compound. At this time, the central element is preferably a transition period metal element from Group 3 to Group 12 or a typical element that easily forms a coordinate bond such as Sr or Pb. Specific examples are shown below, but the compound of the present invention is not limited thereto.

(1) [MoO ₃ S] ^2- (2) [MoO ₂ S ₂ ] ^2- (3) [MoOS ₃ ] ^2- (4) [MoS ₄ ] ^2- (5) [MoO ₃ Se] ^2- (6) [MoO ₂ Se ₂ ] ^2- (7) [MoOSe ₃ ] ^2- (8) [MoSe ₄ ] ^2- (9) [MoS ₃ Se] ^2- (10) [MoS ₂ Se ₂ ] ^2- (11) [MoSSe ₃ ] ^2- (12) [MoOSSe ₂ ] ^2- (13) [MoTe ₄ ] ^2- (14) [WO ₃ S] ^2- (15) [WO ₂ S ₂ ] ^2- (16) [WOS ₃ ] ^2- (17) [WS ₄ ] ^2- (18) [WO ₃ Se] ^2- (19) [WO ₂ Se ₂ ] ^2- (20) [WOSe ₃ ] ^2- (21 ) [WSe ₄ ] ^2- (22) [WS ₃ Se] ^2- (23) [WS ₂ Se ₂ ] ^2- (24) [WSSe ₃ ] ^2-

(25) [WOSSe ₂ ] ^2- (26) [WTe ₄ ] ^2- (27) [ReO ₃ S] ^- (28) [ReO ₂ S ₂ ] ^- (29) [ReOS ₃ ] ^- (30 ) [ReS ₄ ] ^- (31) [VO ₂ S ₂ ] ^3- (32) [VOS ₃ ] ^3- (33) [VS ₄ ] ^3- (34) [VO ₂ Se] ^3- (35) [VOSe ₃ ] ^3- (36) [VSe ₄ ] ^3- (37) [NbS ₄ ] ^3- (38) [NbSe ₄ ] ^3- (39) [TaS ₄ ] ^3- (40) [TaSe ₄ ] ^3- ( _{41) [Fe (MoS 4)} 2] 3- (42) [Fe (WS 4) 2] 3- (43) [Fe (WS 4) 2] 2- (44) [Co (MoO 2 S 2) 2 ^{] 2- (45) [Co (} WS 4) 2] 2- (46) [Co (WOS 3) 2] 2- (47) [Co (WO 2 S 2) 2] 2- (48) [Ni ( MoS ₄ ) ₂ ] ^2-

(49) [Ni (MoOS ₃ ) ₂ ] ^2- (50) [Ni (MoO ₂ S ₂ ) ₂ ] ^2- (51) [Ni (WS ₄ ) ₂ ] ^2- (52) [Ni ( ^{_{WOS 3) 2] 2- (53}} ) [Ni (WO 2 S 2) 2] 2- (54) [Pd (MoS 4) 2] 2- (55) [Pd (WS 4) 2] 2- (56 ) [Pt (MoS ₄ ) ₂ ] ^2- (57) [Pt (WS ₄ ) ₂ ] ^2- (58) [Zn (MoS ₄ ) ₂ ] ^2- (59) [Zn (MoOS ₃ ) ₂ ] ^2- _{(60) [Zn (WS 4} ) 2] 2- (61) [Zn (WOS 3) 2] 2- (62) [Cd (WS 4) 2] 2- (63) [Hg (WS 4) 2] ^2- (64) [Cl ₂ Fe (MoS ₄ )] ^2- (65) [Cl ₂ Fe (WS ₄ )] ^2- (66) [(ON) Fe (WS ₄ )] ^2- (67) [( _{dmf) Fe (WS 4)]} 2- *) (6 ) [(NC) Cu (MoS 4)] 2- (69) [Au ₂ (WS _{4) 2]} ^2- (70) [Au ₂ (WOS _{3) 2]} ^2- (71) [Sn ₂ (WS ₄ ) ₄ ] ^4- (72) (PPh ₃ ) ₃ Ag ₂ (MOS ₄ ) (73) (PPh ₃ ) ₃ Ag ₂ (WS ₄ ) ^*) dmf: dimethylformamide

Since the metal complex ion of the general formula (I) has a negative charge of −2, when the compound containing the general formula (I) as an entire or partial structure is an anion, one or two is required to become a neutral compound. Or 3 counterions are required. The counter ion is preferably an alkali metal ion or ammonium ion. The compound of the present invention can be synthesized with reference to known literature. For example, Inorganica Chimica Actor (I
norganica Chimica Acta), 72, 205 (198)
3), Angewandte Chemi International Edition in English
e, International Edition in English), 20, 934
(1981) and references cited therein.

[MoO _n S _4-n ] ^2- (n = 0-4) is
Depending on the concentration of hydrogen sulfide ions in the aqueous solution, molybdate changes from [MoS ₄ ] ^2- to oxide ions in order, and when sulfide ions do not exist, hydrolysis slowly occurs in sequence. It is known that sulfide ions are changed to oxide ions. Regarding the mechanism, Mark A. Harmaer and A. Geoffrey Sykes, InorganicChemistr
y), 19, 2881 (1980).

The compound of the present invention is dissolved in water or a mixed solvent with a suitable water-miscible organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.). It can be added. The compound of the present invention is preferably added before grain formation, during grain formation, or before chemical sensitization. When it is used during grain formation, it does not depend on the addition method. Specifically, they may be added individually or after being dissolved in a solution such as a halide solution and added gradually, or may be added in a short time.

The amount of the compound of the present invention to be used varies depending on the silver halide grains used, the chemical ripening conditions and the like, but is generally 10 ^-10 to 10 ^-2 mol per mol of silver halide, preferably when used during grain formation. Is about 10 ^-7 to 10 ^-3 mol, and when used during chemical sensitization, it is 10 ^-7 to 10 ^-4 mol.

Regarding the inclusion of the hexacoordinated metal complex in the particles, Japanese Patent Application Laid-Open Nos. 2-20852 and 2-2085 can be used.
3, No. 2-20,854, No. 3-118,535 and No. 3-118,536, the metal ion and the ligand of the hexacoordinated metal complex are the silver ion of the silver halide grain, respectively. It states that it is possible to introduce one or more types of ligands into the crystal lattice by displacing the six halide ions adjacent to it. In the present invention, the VI-valent molybdenum and tungsten metal complexes are tetracoordinated and cannot be introduced into the particles as they are. However, as shown in the example,
Amount of molybdenum complex of 5 × 10 ^-4 mol / molAg was added to the emulsion only at the time of grain formation, and the incorporation rate of halogenated grains obtained by centrifuging was determined by atomic absorption spectroscopy to find that about 20% of molybdenum atoms were incorporated. I understood. It can be seen that the amount of molybdenum is not only adsorbed on the surface but also taken up in the particles. This is because it is known that molybdenum and tungsten are hydrolyzed to have a hexacoordinate octahedral structure when reduced to a V value, and thus a hexadentate complex is formed by a reducing substance such as gelatin. It can be considered to be incorporated into the particle.

In the present invention, sulfur sensitization, selenium sensitization,
Tellurium sensitization, precious metal sensitization and reduction sensitization can be used alone or in combination. Specific examples of the sulfur sensitizer include thiosulfates (eg, sodium thiosulfate, p-toluenethiosulfonate, etc.), thioureas (eg, allylthiourea, N, N ′).
-Diphenylthiourea, triethylthiourea, acetylthiourea, N-ethyl-N '-(4-methyl-2-thiazolyl) thiourea, etc.), thioamides (eg, thioacetamide, N-phenylthioacetamide, etc.), rhodanine Kinds (for example, Rhodanine, N-Ethyl Rhodanine, 5-Benzylidene Rhodanine, 5-Benzylidene-
N-ethyl-rhodanine, diethyl rhodanine, etc.), thiohydantoins, 4-
Oxo-oxazolidine-2-thiones, dipolysulfides, thiosulfonic acids, mercapto compounds such as cysteine, polythionates, elemental sulfur and sodium sulfide have been known.

In addition to the selenium sensitizers described in the prior art, more specifically, selenoureas (eg, selenourea, N, N-dimethylselenourea, N, N-diethyl). Aliphatic selenoureas such as selenoureas, tetramethylselenoureas; N, N, N'-trimethyl-N'-acetylselenoureas, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenoureas, N, N, N'-trimethyl-N'-4-chlorophenylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea,
Substituted selenoureas, etc.), selenoamides (eg,
Selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenoketones (eg, selenoacetone,
Selenoacetophenone, bis- (adamantyl) selenoketone etc.), isoselenocyanates (eg allyl isoselenocyanate etc.), selenocarboxylic acids and esters (eg selenopropionic acid, methyl-3-)
Selenobutylate, etc., selenides (eg, dimethyl selenide, diethyl selenide, triphenylphosphine selenide, etc.), selenophosphates (eg, tri-p-tolyl selenophosphate, etc.), colloidal metal selenium Etc., and about 10 ⁻⁸ to 10 ⁻³ mol may be used per mol of silver halide.

In addition to the tellurium sensitizers described in the prior art, more specifically, colloidal tellurium and telluroureas (eg, allyl tellurourea, N,
N-dimethyl tellurourea, tetramethyl tellurourea, N
-Carboxyethyl-N ', N'-dimethyl tellurourea, N, N'-dimethylethylene tellurourea, N, N'
-Diphenylethylene tellurourea), isotellurocyanates (e.g. allyl isotellurocyanate), telluroketones (e.g. telluroacetone, telluroacetophenone), telluroamides (e.g. telluroacetamide,
N, N-dimethyl tellurobenzamide), tellurohydrazide (for example N, N ′, N′-trimethyltelulobenzhydrazide), telluroester (for example t-butyl-t)
-Hexyl telluroester), phosphine tellurides (eg tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), other tellurium compounds (eg United Kingdom There are, for example, negatively charged telluride ion-containing gelatin described in Japanese Patent No. 1,295,462, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, allyl tellurocyanate), etc., per mol of silver halide, 10 ^{-8 to} 5 x 10 ^-3
It may be used in moles.

In noble metal sensitization, gold, platinum, palladium
Can be used in combination with precious metal sensitizers such as um and iridium
it can. In this case, it is particularly preferable to use a gold sensitizer together.
Specifically, chloroauric acid, potassium chloroaure
G, potassium aurithiocyanate, gold sulfide, gold serena
Id, etc., and is 10 per mol of silver halide. ^-7
-10^-2Molar amounts can be used.

In the present invention, a reduction sensitizer may be used in combination. Specifically, stannous chloride, aminoiminomethanesulfinic acid, a hydrazine derivative, a borane compound, a silane compound, a polyamine compound, etc. may be used. Can be mentioned.

The silver halide emulsion used in the present invention is
Silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride are preferred. The silver halide grains used in the present invention have a regular crystal form such as a cube and an octahedron, and an irregular crystal form such as a sphere and a plate. Or a compound 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. Even if the silver halide grains used in the present invention have different layers from the inside and the surface layer,
It may consist of a uniform layer. Iodine composition differs between the inside and the surface of the particle (especially, the iodine content is higher inside)
2- to multi-structured particles are also preferred. It may also be a grain in which a latent image is mainly formed (for example, an internal latent image type emulsion, a pre-fogged direct inversion type emulsion). 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, and an average aspect ratio of 3
A tabular grain emulsion in which the above grains account for 50% or more of the total projected area is also preferable. The silver halide emulsion used in the present invention has a statistical coefficient of variation (value S / d obtained by dividing the standard deviation S by the diameter d in the distribution represented by the diameter when the projected area is approximated by a circle) of 20. A monodisperse emulsion having a content of not more than 0.1% is particularly preferable. Also, two or more emulsions may be mixed.

The photographic emulsions used in the present invention include P. Glafkides, Chimie er Physique Photograp.
heque) (published by Paul Montel, 1967), Gee
Photographic Emuls by GF Duffin
ion Chemistry) (Published by Focal Press, 1966)
, VL Zelikman et al., Making and Coating Photograp
Hic Emulsion) (Focal Press, 1964) and the like can be used.

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, cadmium salt, zinc salt, thallium salt, iron salt or complex salt thereof,
A ruthenium salt or a complex salt thereof, an osmium salt or a complex salt thereof, a cobalt salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof may be present together.

As the binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material using the silver halide photographic emulsion produced in the present invention, it is advantageous to use gelatin, but other than that. 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, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various synthetic hydrophilic polymer substances such as polyvinyl imidazole and polyvinyl pyrazole can be used as single or copolymers. As gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin and the Japan Photographic Society of Science (Bull. Soc. Phot. Japan), 16, 30 (196)
The enzyme-treated gelatin as described in 6) may be used, or a hydrolyzate of gelatin may be used.

The photosensitive material using the silver halide photographic emulsion produced in 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 halogenated compounds (2,4-dichloro-6-hydroxy-1,3,3
5-triazine and its sodium salt) and an active vinyl compound (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ether or vinylsulfone group Vinyl-based polymers having side chains) are preferable because they rapidly cure hydrophilic colloids such as gelatin and give stable photographic characteristics. N-carbamoylpyridinium salts (such as (1-morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (such as 1- (1-chloro-1-pyridinimethylene) pyrrolidinium-2naphthalenesulfonate) also have a curing rate. Good early.

The silver halide photographic emulsion produced according to 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 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 nucleus group (for example, US Pat. Nos. 2,933,390 and 3,3,390).
635,721), an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,51).
No. 0), cadmium salt, azaindene compound and the like. U.S. Pat. No. 3,615,613
No. 3,615,641, No. 3,617,295
No. 3,635,721, the combination is particularly useful.

The silver halide photographic emulsion produced by the present invention contains various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be included. 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, benzene sulfinic acid, known as antifoggants or stabilizers such as benzenesulfonic acid amide, can be added to many compounds.

The light-sensitive material using the silver halide photographic emulsion produced in the present invention is a coating aid, antistatic, anti-slip property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, hardening, sensitization) One or more surfactants may be included for various purposes such as).

Further, the light-sensitive material using the silver halide photographic emulsion produced in the present invention contains a water-soluble dye in the water-soluble colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. May be included. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanine dyes are also useful. . The oil-soluble dye may be emulsified by an oil-in-water appropriate dispersion method and added to the water-immersive 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, any emulsion layer having the same color sensitivity may be corrected from 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. Generally, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances. 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 light-sensitive material using the silver halide photographic emulsion produced in the present invention. Specific examples thereof include Research Disclosure (RD) No. 17643, VII-C to G. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and Japanese Patent Publication No. 58-10739.
British Patent Nos. 1,425,020 and 1,476,7
Those described in No. 60 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, No. 3,725,067, Research Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630.
Nos. 4,540,654 are preferable.
Examples of cyan couplers include phenol-type and naphthol-type couplers, and examples thereof include US Pat. No. 4,052,
No. 212, No. 4,146, 396, No. 4,22
No. 8,233, No. 4,296,200, No. 2,3
69,929, 2,801,171, 2,
772, 162, 2, 895, 826, 3,772, 002, 3,758, 309, 4, 334, 011 and 4, 327, 173.
West German Patent Publication No. 3,329,729, European Patent No. 12
No. 1,365A, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559,
No. 4,427,767, European Patent 161,626.
Those described in No. A are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in, for example, Research Disclosure No. 17643, Section VII-G, U.S. Pat. No. 4,1.
63,670, Japanese Examined Patent Publication No. 57-39413, U.S. Pat. Nos. 4,004,926 and 4,138,258,
Those described in British Patent 1,146,368 are preferred.

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. DIR couplers that release development inhibitors are described in Research Disclosure No. 17643 VII
Patents described in section F, JP-A-57-151944
No. 57-154234, No. 60-184248.
Those described in U.S. Pat. No. 4,248,962 are preferred. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent 2,
097,140, 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers which can be used in a light-sensitive material using the silver halide photographic emulsion produced in the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. 4,283,472
No. 4, No. 4,338,393, No. 4,310,61
No. 8, etc., multi-equivalent couplers, JP-A-60-1859.
50, DIR redox compounds or DIR coupler releasing couplers described in JP-A No. 50-24252,
Research Disclosure No. 5, a coupler which releases a dye that recovers color after separation described in European Patent No. 173302A. 11449, 24241, JP-A-61-201
Examples thereof include bleaching accelerator releasing couplers described in US Pat. No. 247, and ligand releasing couplers described in US Pat. No. 4,553,477.

The coupler used in the light-sensitive material using the silver halide photographic emulsion produced in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,0.
No. 27 and the like. Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, cyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl). Phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate,
Bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tri Dodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di-2
-Ethylhexyl phenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate,
Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isoform). Stearyl alcohol,
2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl))
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate) aniline derivative (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (for example, paraffin , Dodecylbenzene, diisopropylnaphthalene) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

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

In the light-sensitive material using the silver halide photographic emulsion produced in the present invention, the photographic emulsion layer and other layers are plastic films usually used for photographic light-sensitive materials,
It is applied to a flexible support such as paper or cloth or a rigid support such as glass, registry, metal or the like. What is useful as a 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, polycarbonate, a baryter layer or α.
-Paper coated with or laminated with an olefin polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer) or the like. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with the photographic emulsion layers. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, 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 a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method can be used. US Patent No. 2, as required
Multiple layers may be simultaneously coated by the coating method described in No. 681,294, No. 2,761,791, No. 3,526,528, and No. 3,508,947.

The present invention can be applied to the production of light-sensitive materials using various color and black and white silver halide photographic emulsions. 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) or by utilizing a tri-color coupler mix, or in U.S. Pat. No. 4,126,46.
The present invention can be applied to a black-and-white light-sensitive material for X-ray or the like by utilizing a black color coupler described in No. 1 and British Patent No. 2,102,136. Film for plate making such as squirrel film or scanner film,
The present invention can be applied to direct / indirect medical or industrial X-ray films, negative black and white films for photography, black and white photographic paper, COM or ordinary microfilm, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials. .

When the silver halide photographic emulsion produced by the present invention is applied to the color diffusion transfer photographic method, it is a peeling type or Japanese Patent Publication No. 46-16356.
The peeling-free type film unit as described in JP-A-48-33697, JP-A-50-13040 and British Patent 1,330,524 can have rigidity. The use of a polymeric acid layer protected by a neutralization timing layer in any of the above types of formats is advantageous for widening the processing temperature latitude. When used in a color diffusion transfer photographic method, it may be added to any layer in the light-sensitive material, or may be used as a developing solution component by being sealed in a processing solution container.

Various exposure means can be used for the light-sensitive material using the silver halide photographic emulsion produced in the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the irradiation light source or the 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. A gas, a dye solution or a semiconductor laser, a light emitting diode, or a plasma light source which emits light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a linear or planar micro-shutter array using a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam, liquid crystal (LCD), lanthanum-doped lead titan zirconate (PLZT), or the like. It is also possible to use an exposure means combining the above light sources. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used for developing the light-sensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful,
A p-phenylenediamine compound is preferably used,
As typical examples thereof, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonic acid Examples include salt. 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 usually 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, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphos. Various chelating agents represented by nocarboxylic acid, West German Patent Application (OLS) No. 2,622,950
You may add the antioxidant etc. which are described in Japanese to a color developing solution.

In the development processing of a 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 hytroquinone, 1
Known black-and-white developers such as 3-pyrazolidones such as -phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process,
It may be done individually. To further speed up processing,
A processing method of performing a bleach-fixing process after the bleaching process may be used. Examples of bleaching agents include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids,
Quinones, nitrone compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (III
) Or an organic complex salt of cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, aminopolycarboxylic acid such as 1,3-diamino-2-propanoltetraacetic acid or citric acid, tartaric acid, malic acid, etc. A complex salt of an organic acid; persulfate; manganate; nitrosophenol and the like can be used.
Of these, ethylenediaminetetraacetic acid iron (III) salt, diethylenetriaminepentaacetic acid (III) 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 a stand-alone bleaching solution and a 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, Kaisho 53-32736, No. 53-57831, No. 3
7-418, 53-65832, 53-726.
No. 23, No. 53-95630, No. 53-95631.
No. 53-104232, No. 53-124424
No. 53-141623, No. 53-28426,
Research Disclosure, No. 17129 (1
Compounds having a mercapto group or a disulfide group as described in, for example, July 1978); thiazolidine derivatives as described in JP-A-50-140129; JP-B-45.
-8506, JP-A-52-20832, 53-3
2735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide described in JP-A-58-16235; West German Patent 966,410. Polyethylene oxides described in JP-A No. 2,748,430; polyamine compounds described in JP-B-45-8836; Others JP-A-49-4243
No. 4, No. 49-59644, No. 53-94927,
54-35727, 55-26506 and 58-163940, and the compounds and iodides thereof,
Bromide ions can also be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858.
, West German Patent No. 1,290,812, JP-A-53-9
The compounds described in 5630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the sensitizer. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodides, but thiosulfates are generally used. As the bleach-fixing solution and the preservative for the fixing solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

After bleach-fixing treatment or fixing treatment, washing treatment and stabilizing treatment are usually carried out. For the purpose of preventing precipitation and saving water during the washing process and stabilization process,
Various known compounds may be added. For example, in order to prevent precipitation, a water softener such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, organic phosphoric acid,
Insecticides and antifungal agents that prevent the generation of various bacteria, algae, and mold, metal salts represented by magnesium salts, aluminum salts, and bismuth salts, or surfactants that prevent drying load and unevenness, and various A hardener and the like can be added as necessary. Or West, Photographic Science and Engineering Magazine (LE West, Phot. Sci. Eng.), Volume 6, 344
The compounds described in (1965) and the like may be added. In particular, it is effective to add a chelating agent or an antifungal agent.

In the water washing step, two or more layers of 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.), insecticides (benzisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol,
Various additives such as a sulfanilamide and benzotriazole), a surfactant, an optical brightener and a hardener may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjusting agent after the treatment. Further, in the case of the color sensitizer for photographing, the usual (washing-stabilizing) step after fixing can be replaced with the above-mentioned stabilizing step and washing step (water-saving treatment). On this occasion,
If the magenta coupler is 2 equivalents, the formalin in the stabilizing bath may be removed. The washing and stabilizing treatment time is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, which may vary depending on the type of the photosensitive material and the processing conditions.

The color light-sensitive material using the silver halide emulsion produced in 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, indoaniline compounds described in U.S. Pat. No. 3,342,592, No. 3,342,599,
Research Disclosure, No. 14850 and No. Schiff base type compound described in 15159, N
o. The aldol compound described in 13924, the metal complex described in US Pat. No. 3,719,492, and JP-A-53-1.
Starting with the urethane compounds described in No. 35628,
JP-A-56-6235, JP-A-56-16133 and JP-A-56-5
6-59232, 56-67842, 56-8
No. 3734, No. 56-83735, No. 56-8373.
No. 6, No. 56-89735, No. 56-81837,
56-54430, 56-106241, 5
6-107236, 57-97531 and 5
Examples thereof include various salt type precursors described in 7-83565 and the like. The silver halide color light-sensitive material may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of promoting color development. Typical compounds are disclosed in JP-A-56-64339 and JP-A-5-63339.
7-144547, 57-211147, 58
-50532, 58-50536, 58-50
No. 533, No. 58-50534, No. 58-50535.
No. 58-115438 and the like.

Various processing solutions are used at 10 to 50 ° 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. Also, for saving silver in the light-sensitive material, West German Patent No. 2,226,770 or US Pat. No. 3,67
Treatment using cobalt intensification or hydrogen peroxide intensification described in 4,499 may be performed. If necessary, heaters, temperature sensors, liquid level sensors,
A circulation pump, a filter, a floating pig, a squeegee, etc. may be provided. 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 is a color paper, it can be generally bleach-fixed if necessary, and also when the light-sensitive material is a color photographic material for photographing.

[0063]

EXAMPLES Specific examples of the present invention will be given below. Example 1 0.05 g of calcium bromide and gelatin 2 kept at 75 ° C
Side length 0.2 in 1 liter of pH 5.0 solution containing 5 g
While stirring with seed crystals of monodisperse silver bromide cubic grains of μm, an aqueous solution of silver nitrate (AgNO ₃ 196 g), an aqueous solution of potassium bromide (137 g) and an aqueous solution containing the compounds of the types and addition amounts shown in Table 1 were tripled. The jets were added simultaneously over 80 minutes at a constant flow rate. Meanwhile, the silver potential was kept at +120 mV against the saturated calomel electrode.

After the completion of grain formation, desalting was carried out by an ordinary flocculation method, washing with water was carried out, and then gelatin and water were added. The obtained silver bromide emulsion is a monodisperse cubic emulsion having a side length of 0.5 μm. The molybdenum and tungsten concentrations of the prepared emulsion and the supernatant aqueous solution obtained by centrifuging the emulsion were determined by the atomic absorption method. From the difference, the amounts of molybdenum and tungsten incorporated in the particles were obtained. As a result, it was found that about 20% of the added tungsten or molybdenum was incorporated in the particles. To this emulsion, gelatin, sodium dodecylbenzene sulfonate was added, and gelatin was added onto a triacetyl cellulose film support having an undercoat layer.
Polymethylmethacrylate particles, 2,4-dichloro-6
It was applied by extrusion with a protective layer containing sodium hydroxy-s-triazine.

These samples were exposed to sensitometric exposure (1 second and 10 ⁻³ seconds) through an optical wedge, and then,
After development with a MAA-1 developer having the following formulation for 10 minutes at 20 ° C., the product was stopped, fixed, washed with water and dried by a conventional method, and the optical density was measured. The relative sensitivity was represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog + 0.1. The gradation was determined by the gradient from the optical density of fog +0.1 of the characteristic curve to the optical density of fog +1.1. That is, the optical density difference of 1.0 was calculated by dividing the relative exposure amount that gives an optical density of fog +1.1 by the relative exposure amount that gives an optical density of fog +0.1. Here, the sensitivity and gradation are expressed with the value of the emulsion in which the compound is not added as 100.

[0066]

[Table 1]

Comparative Compound A: Ammonium hexachloroiridate (III) 〃 B: Potassium hexabromide (III) 〃 C: Potassium hexacyanoruthenate (II)

MAA-1 developer 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g KBr 1.0 g Water was added to 1 liter

As is clear from Table 1, the silver halide emulsion containing the metal complex of the present invention has high sensitivity and gradation in both low and high light exposure. It can be seen that the effect is particularly great in high-illuminance exposure.

Example 2 To the silver bromide emulsion prepared in Example 1, sodium thiosulfate was added at 3.9 × 10 ^-5 mol per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes.
A minute heat was applied for chemical aging. Then gelatin, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, sodium dodecylbenzene sulfonate was added to form gelatin, polymethylmethacrylate particles, 2, on a triacetyl cellulose film support having an undercoat layer. It was applied by extrusion with a protective layer containing 4-dichloro-6-hydroxy-s-triazine sodium salt.

These samples were exposed for sensitometry and developed in the same manner as in Example 1. Here, the sensitivity and gradation are shown as 100 in the same manner as in Example 1 in the case of the emulsion in which the metal complex is not added.

[0072]

[Table 2]

From Table 2, the silver halide emulsion incorporating the metal complex of the present invention has a high sensitivity and a high gradation without depending on the exposure illuminance, and a great effect can be obtained particularly in the exposure with high illuminance.

Example 3 The emulsion prepared in Example 1 was heated to 56 ° C., sodium thiosulfate (6 × 10 ^-6 mol / mol Ag), chloroauric acid (8
× 10 ^-6 mol / mol Ag) and potassium thiocyanate (8 × 10 ^-4 mol / mol Ag) were added, and chemical sensitization was performed for 60 minutes. Then gelatin, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetraazaindene, sodium dodecylbenzene sulfonate was added to the triacetyl cellulose film support having a subbing layer,
It was applied by extrusion with a protective layer containing gelatin, polymethylmethacrylate particles, 2,4-dichloro-6-hydroxy-s-triazine sodium salt.

These samples were exposed and developed for sensitometry in the same manner as in Example 1. Here, the sensitivity and gradation are shown as 100 in the same manner as in Example 1 in the case of the emulsion in which the metal complex is not added.

[0076]

[Table 3]

From Table 3, the silver halide emulsions incorporating the metal complex of the present invention have a high sensitivity and a high gradation without depending on the exposure illuminance even when used in combination with gold sulfur sensitization, and are particularly large in exposure to high illuminance. It can be seen that the effect can be obtained.

Example 4 While stirring in 850 ml of an aqueous solution of pH 5.0 containing sodium chloride (4.5 g) and gelatin (25 g) kept at 50 ° C., an aqueous silver nitrate solution (AgNO ₃ 5.0 g) and an aqueous sodium chloride solution (1. 7 g) were added simultaneously at a constant flow rate over 10 minutes. After that, an aqueous solution of silver nitrate (AgNO ₃
119.8 g), aqueous sodium chloride solution (41.1 g)
And the aqueous solution containing the metal complex of the present invention was simultaneously added at a constant flow rate over 25 minutes by a triple jet.

After the completion of grain formation, desalting was carried out by an ordinary flocculation method, the mixture was washed with water, and gelatin and water were added. The obtained silver chloride emulsion is a monodisperse cubic emulsion having a side length of 0.5 μm.

After coating on a support and exposing in the same manner as in Example 2, development was carried out at 20 ° C. for 5 minutes with a developing solution having the following formulation, and then stopped, fixed, washed with water and dried by a conventional method, and the density was measured.
Here, the sensitivity and gradation are expressed with the value of the emulsion in which the metal complex is not added as 100.

[0081]

[Table 4]

Developer Formulation Metol 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g NaCl 0.58 g Water was added to 1 liter

As is clear from Table 4, even in the silver chloride emulsion, when the metal complex of the present invention was introduced, high sensitivity and high gradation were achieved under both low illuminance and high illuminance. In particular, the effect of exposure with high illuminance was remarkable.

Example 5 Ammonium nitrate (125 g) kept at 60 ° C.
Nia (31.3g), potassium bromide (51g) and gelatin
While stirring in 25 liters of an aqueous solution containing 500 g of
Aqueous silver nitrate solution (AgNO₃4408 g) and potassium bromide
Aqueous um solution (3088g) was added simultaneously over 50 minutes
did. After that, an aqueous solution of silver nitrate (AgNO ₃4492
g), potassium bromide aqueous solution (3150 g) for 50 minutes
And added simultaneously. Saturation of silver potential during grain formation
It was kept at -40 mV against the Japanese calomel electrode.

After the completion of grain formation, desalting was carried out by an ordinary flocculation method, and after washing with water, gelatin and water were added. The obtained silver bromide emulsion is a monodisperse octahedral emulsion having a side length of 0.85 μm.

This emulsion was divided into small portions, the compounds shown in Table 5 were added, and chemical ripening was carried out at 60 ° C. for 60 minutes. Then magenta coupler; 3- {3- [2- (2,4-di-te
rt-Amylphenoxy) butyrylamino] benzoylamino} -1- (2,4,6-trichlorophenyl) pyrazolin-5-one

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 extrusion onto a triacetyl cellulose film support having a subbing layer with a gelatin protective layer containing polymethylmethacrylate microparticles. Exposure of these samples for sensitometry (1 second and 10 ^-3 seconds)
And the following color development processing was performed. The density of the treated sample was measured with a green filter. The relative sensitivity is
It was expressed as a relative value of the reciprocal of the exposure amount required to obtain an optical density of fog + 0.1. The gradation is the fog of the characteristic curve +0.
From the optical density of 1 to the optical density of fog + 1.1, the gradient was obtained. That is, an optical density difference of 1.0 will cause fog +
From the relative exposure amount that gives an optical density of 1.1, fog +0.
It was determined by dividing by the relative exposure amount that gives an optical density of 1. Here, the sensitivity and gradation are expressed with the value of the emulsion in which the compound is not added as 100.

[0092]

[Table 5]

The developing process used here is 38 under the following conditions.
Performed at ° C. 1. Color development 2 minutes 45 seconds 2. Bleach 6 minutes 30 seconds 3. Washing with water 3 minutes 15 seconds 4. Fixed arrival 6 minutes 30 seconds 5. Washing with water 3 minutes 15 seconds 6. Stability 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-Methyl-aniline sulfate 4.5 g Water added to 1 liter

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 was added to 1 liter

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

Stabilizer Formalin 8.0 ml Add water to 1 liter

From Table 5, the emulsion to which the metal complex of the present invention was added at the time of chemical ripening has high sensitivity in both low and high light exposure.
It can be seen that high gradation can be obtained, and the effect is particularly great when exposed to high illuminance.

Example 6 An aqueous solution of silver nitrate (AgNO ₃ 2503 g) was added to 25 liters of an aqueous solution containing ammonium nitrate (125 g), ammonia (31.3 g), potassium bromide (5.4 g) and gelatin (500 g) kept at 60 ° C. ) And aqueous potassium bromide solution (1098 g) were added simultaneously over 50 minutes. Then, a silver nitrate aqueous solution (AgNO ₃ 2503
g) and an aqueous potassium bromide solution (1750 g) were added simultaneously over 50 minutes. The silver potential was maintained at +60 mV against the saturated calomel electrode during grain formation.

After completion of grain formation, desalting and washing with water were carried out by a usual flocculation method, and then gelatin and water were added. The obtained silver bromide emulsion is a monodisperse cubic emulsion having a side length of about 0.84 μm.

This emulsion was divided into small portions and heated to 56 ° C.,
Compounds shown in Table 6, chloroauric acid (8 × 10 ⁻⁶ mol / mol A
g) and potassium thiocyanate (8 × 10 ⁻⁴ mol / mol Ag) were added, and chemical sensitization was performed for 60 minutes. afterwards,
A coated sample was prepared under the same conditions as in Example 5, and the same exposure and development as in Example 5 were performed. The density of the treated sample was measured with a green filter. The relative sensitivity was represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog + 0.1. The gradation was determined by the gradient from the optical density of fog +0.1 of the characteristic curve to the optical density of fog +1.1. That is, the optical density difference of 1.0 was calculated by dividing the relative exposure amount that gives an optical density of fog +1.1 by the relative exposure amount that gives an optical density of fog +0.1. Here, the sensitivity and gradation are expressed with the value of the emulsion in which the compound is not added as 100.

[0102]

[Table 6]

From Table 6, also in the silver bromide cubic emulsion,
According to the present invention, high sensitivity and high gradation can be obtained in both low illuminance and high illuminance exposure, and it can be seen that the effect of the present invention is great especially in high illuminance exposure. From this, it was shown that the effect obtained by adding the metal complex of the present invention did not depend on the crystal habit of the emulsion. Furthermore, it has been found that the effects of the present invention are not impaired even when the metal complex of the present invention and a noble metal sensitizer are used in combination.

[0104]

According to the present invention, it is possible to provide a silver halide photographic emulsion having high illuminance, higher sensitivity, and less dependency on exposure illuminance.

Claims (1)

[Claims] 1. A process for producing a silver halide photographic emulsion, which comprises using a compound containing at least one metal complex ion represented by the following general formula (I) as a whole or partial structure. General formula (I) [MX _n Y _4-n ] ^{m-In the} formula, M represents molybdenum, tungsten, rhenium, vanadium, niobium or tantalum, X and Y are oxygen,
Represents sulfur, selenium or tellurium, n is 0 to 4, m
Represents a number from 1 to 3. However, at least one of X and Y represents sulfur, selenium, or tellurium.