JP2794250B2 - Method for producing silver halide photographic emulsion - Google Patents

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 Silver halide photographic materials are subjected to chemical sensitization by using various chemical sensitizers to obtain high-sensitivity and high-quality images. For example, it is desired to further enhance the sensitivity and image quality by incorporating a metal complex into the particles, or adding the metal complex after the particles are formed and fixing the particles to the surface.

A technique for introducing or introducing a metal complex at any stage immediately before emulsion preparation and coating is disclosed in US Pat.
No. 060. The metal complex at this time is represented by the general formula R ₂ MX ₆ , wherein R represents a hydrogen, an alkali metal or an ammonium group, and M represents a transition group metal of a platinum group except osmium, for example, platinum, palladium, iridium, rhodium, ruthenium. And X represents a halogen atom, such as chlorine or bromine. These metal complexes are water-soluble and, when introduced, have an effect as an antifoggant and a stabilizer, but palladium (IV value)
Shows that sensitization can be achieved when a hexacoordinate metal complex of the formula (1) is added.

[0004] Many examples of hexacoordinate metal complexes having a halide ion as a ligand have been known since then. In recent years other ligands of halide ions such as nitrosyl, thionitrosyl, carbonyl, cyanide, thiocyanide, selenocyanide, tellurocyanide, azide, oxide, sulfite and nitrite Regarding (including nitrite), it has been reported that a six-coordinate metal complex is introduced into particles. For example, JP-A Nos. 2-20,854, 2-20, 85
No. 3, 2-20, 852, 2-20, 855, 3 118, 535, 3 118, 535, 4
-97,337.

Further, in US Pat. No. 4,997,751 and JP-A-3-15,040, a low illuminance is obtained by using a metal complex of iridium as a chemical sensitizer after grain formation and fixing it near the grain surface. Improving failure.

However, the use of these metal complexes in or after the formation of particles is effective in improving low-light illumination failure and increasing gradation, but is particularly disadvantageous in high-light illumination failure and sensitivity. . Further, in these patents, there is no description about sulfide ions, and all of the metal complexes used have a six-coordinate octahedral structure, and those having a four-coordinate tetrahedral structure are described. Not.

In addition, chemical sensitization is usually performed using various chemical substances not containing heavy metals in order to obtain desired sensitivity, gradation, and the like. A typical method is sensitization of chalcogenides such as sulfur, selenium and tellurium. The most basic of these is a sulfur sensitization method using a so-called unstable sulfur compound that can react with silver ions to form silver sulfide. Specifically, P. Grafkide
s, Chimie et Physique Photographique (Paul Mont
el company, 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)
And so on.

In 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 No. 2-130976, 2-229300
No. 2-272879, No. 3-53693, No. 3
Compounds described in JP-A-82929 and the like are shown.

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

[0010] These chalcogenide sensitizations have disadvantages such as a large change in sensitivity gradation due to exposure illuminance under environmental conditions during chemical sensitization, and particularly low high illuminance sensitivity.

The use of a compound containing a metal complex ion such as molybdenum or tungsten similar to that of the present invention is disclosed in British Patent No. 385,545 and US Pat.
No. 7, this is only for silver molybdate or silver tungstate and is not known to be used for 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 high sensitivity and high image quality. An object of the present invention is to provide a method for producing a silver halide photographic emulsion having high illuminance sensitivity and low dependence on exposure illuminance.

[0013]

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

Among 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 be a ligand of 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. The central element at that time is preferably a transition period metal element from Group 3 to Group 12 or a typical element that easily generates a coordinative bond such as Sr and Pb. Specific examples are shown below, but the compounds of the present invention are 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 a whole or a partial structure is an anion, it is necessary that one or two One or three counterions are required. The counter ion is preferably an alkali metal ion or an ammonium ion. The compound of the present invention can be synthesized with reference to known literature. For example, Inorganica Timica Acta (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.

[0019] _{[MoO n S 4-n]} 2- (n = 0-4) are
In the aqueous solution, oxide ions are sequentially changed from molybdic acid to [MoS ₄ ] ^2- in accordance with the concentration of hydrogen sulfide ions, and sulfide ions are sequentially changed. In the absence of sulfide ions, hydrolysis is sequentially sequentially performed. It is known that sulfide ions are changed to oxide ions. Mark A. Harmaer and A. Geoffrey Sykes discuss the mechanism in 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 (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). Can be added. The compound of the present invention is preferably added before or during grain formation or before chemical sensitization. When used at the time of particle formation, it does not depend on the method of addition. Specifically, it may be added alone or dissolved in a solution such as a halide solution, and may be added gradually or in a short time.

The amount of the compound of the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but it 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 for chemical sensitization, 10 ^-7 to 10 ^-4 mol is used.

Regarding the inclusion of a hexacoordinate metal complex in the particles, see JP-A Nos. 2-20,852 and 2-20,85.
In Nos. 3, 2, 20, 854, 3-118, 535 and 3-118, 536, the metal ion and the ligand of the hexacoordinate metal complex are respectively the same as the silver ion of the silver halide grains. It states that one or more types of ligands can be introduced into the crystal lattice by altering the six halide ions adjacent thereto. In the present invention, the metal complex of VI-valent molybdenum and tungsten is tetracoordinate, and it is impossible to introduce the metal complex into the particles as it is. However, as shown in the example,
The molybdenum complex was added in an amount of 5 × 10 ⁻⁴ mol / molAg only when forming the grains. When the incorporation rate of the halogenated grains obtained by centrifugation of the emulsion was determined by the atomic absorption method, it was found that about 20% of molybdenum atoms were incorporated. I understood. It can be seen that the amount of molybdenum is not only simply adsorbed on the surface but also incorporated into the particles. This is because it is known that molybdenum and tungsten undergo a reduction to a V value and undergo hydrolysis to form a six-coordinate octahedral structure. It can be considered to be incorporated into the particles.

In the present invention, sulfur sensitization, selenium sensitization,
Tellurium sensitization, noble metal sensitization and reduction sensitization can be used alone or in combination. Specific compounds for 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 (Eg, rhodanine, N-ethyl rhodanine, 5-benzylidene rhodanine, 5-benzylidene-
N-ethyl-rhodanine, diethyl rhodanine, etc.), as well as thiohydantoins,
Also known are oxo-oxazolidine-2-thiones, dipolysulfides, thiosulfonic acids, mercapto compounds such as cysteine, polythionates, elemental sulfur, sodium sulfide and the like.

Further, in the selenium sensitizer, in addition to those described in the prior art, more specifically, selenoureas (eg, selenourea, N, N-dimethylselenourea, N, N-diethyl) Aliphatic selenoureas such as selenourea and tetramethylselenourea; N, N, N′-trimethyl-N′-acetylselenourea, N, N, N′-trimethyl-N′-heptafluoropropylcarbonylselenourea; N, N, N'-trimethyl-N'-4-chlorophenylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea,
Etc.), selenoamides (for example,
Selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenoketones (for example, selenoacetone,
Selenoacetophenone, bis- (adamantyl) selenoketone, etc.), isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenocarboxylic acids and esters (eg, selenopropionic acid, methyl-3-)
Selenobutyrate, etc.), selenides (eg, dimethyl selenide, diethyl selenide, triphenylphosphine selenide, etc.), selenophosphates (eg, tri-p-tolylselenophosphate, etc.), colloidal metal selenium And the like may be used in an amount of about 10 ^-8 to 10 ^-3 mol per mol of silver halide.

The tellurium sensitizers include, in addition to those described in the prior art, more specifically, colloidal tellurium and tellureas (for example, allyltellurourea, N,
N-dimethyltellurourea, tetramethyltellurourea, N
-Carboxyethyl-N ', N'-dimethyltellurourea, N, N'-dimethylethylenetellurourea, N, N'
Diphenylethylene tellurourea), isotellurocyanates (e.g. allyl isotellurocyanate), telluroketones (e.g. telluroacetone, telluroacetophenone), telluroamides (e.g. telluroacetamide,
N, N-dimethyltellurobenzamide), tellurohydrazide (eg, N, N ′, N′-trimethyltellurobenzhydrazide), telluroester (eg, t-butyl-t)
-Hexyl telluride esters), phosphine tellurides (e.g. tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), other tellurium compounds (e.g. UK) Patent No. 1,295,462, negatively charged telluride ion-containing gelatin, potassium telluride, potassium tellurocyanate, sodium telluropentathionate, allyl tellurocyanate), etc. 10 ^{-8 to} 5 × 10 ^-3
It may be used in moles.

In the noble metal sensitization, gold, platinum, palladium
Iridium and other precious metal sensitizers
it can. In this case, it is particularly preferable to use a gold sensitizer in combination.
Specifically, chloroauric acid, potassium chloroauray
G, potassium aurithiocyanate, gold sulfide, gold selena
And 10 mol per mol of silver halide. ^-7
-10^-2About moles can be used.

In the present invention, a reduction sensitizer can be used in combination, and specific examples thereof include stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, and the like. No.

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 cubic or octahedral, or have an irregular crystal form such as spherical or plate-like. Or a compound having a complex 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. Even when the silver halide grains used in the present invention have different layers from the inside and the surface,
It may consist of a uniform layer. The iodine composition is different between the inside of the particle and the surface layer (especially, the iodine content is higher inside)
Two- to multi-structure particles are also preferred. Further, the grains may mainly form a latent image (for example, an internal latent image type emulsion, and a directly fogged direct reversal type emulsion). Preferably, the particles are such that the latent image is mainly formed on the surface. The silver halide emulsion used in the present invention has a thickness of 0.5 μm or less, preferably 0.3 μm or less, a diameter of preferably 0.6 μm or more, and an average aspect ratio of 3 μm or less.
Tabular grain emulsions in which the above grains account for 50% or more of the total projected area are also preferred. The silver halide emulsion used in the present invention has a statistical coefficient of variation (a value S / d obtained by dividing the standard deviation S by the diameter d in the distribution expressed by the diameter when the projected area is approximated by a circle) is 20. % Is particularly preferred. Further, two or more emulsions may be mixed.

The photographic emulsion used in the present invention includes Chimie Physique Photograp by P. Glafkides.
heque) (Paul Montell, 1967);
Photographic Emuls by GF Duffin
ion Chemistry) (Focal Press, 1966)
Making and Coating Photograp, VL Zelikman et al.
hic Emulsion) (Focal Press, 1964) and the like.

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

Gelatin is advantageously used as a binder or protective colloid which can be used in an emulsion layer or an intermediate layer of a light-sensitive material using a silver halide photographic emulsion produced in the present invention. 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 hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinylimidazole and polyvinylpyrazole can be used. As the gelatin, besides general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japan Society of Science Photography (Bull. Soc. Phot. Japan), 16, 30 (196)
Enzyme-treated gelatin as described in 6) may be used, or a hydrolyzate of gelatin may be used.

In the light-sensitive material using the silver halide photographic emulsion produced in the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples thereof include chromium salts, aldehyde salts (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol-based compounds (dimethylol urea, etc.). Active halide (2,4-dichloro-6-hydroxy-1,3,3)
5-triazine and its sodium salt and the like and an active vinyl compound (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ether or vinylsulfone group Vinyl-based polymer having a side chain) is preferred because it rapidly cures a hydrophilic colloid such as gelatin and provides stable photographic properties. N-carbamoylpyridinium salts (such as (1-morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (such as 1- (1-chloro-1-pyridinmethylene) pyrrolidinium-2-naphthalenesulfate) also have a high curing rate. Excellent early.

The silver halide photographic emulsion produced in the present invention may be spectrally sensitized with methine dyes or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, the pyrroline nucleus is an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus,
An oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, ie, , Indolenine nucleus, benzindolenin 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. In a merocyanine dye or a complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidin-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbenzene compound which is a nitrogen-containing heterocyclic nucleus group (for example, US Pat. Nos. 2,933,390 and 3,333)
635,721), formaldehyde condensates of aromatic organic acids (for example, US Pat. No. 3,743,51).
0), cadmium salts, azaindene compounds and the like. U.S. Pat. No. 3,615,613
Nos. 3,615,641 and 3,617,295
No. 3,635,721 are particularly useful.

The silver halide photographic emulsion prepared according to the present invention may contain various compounds for the purpose of preventing fog during the production process of the photographic material, storage or photographic processing, and stabilizing photographic performance. Can be contained. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, and aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes) and pentaazaindenes ; Benzenethiosulfonate, 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 can be used as a coating aid, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (for example, development acceleration, high contrast, sensitization). ) And may contain one or more surfactants for various purposes.

The light-sensitive material using the silver halide photographic emulsion produced in the present invention may be used as a filter dye or in a water-immersed colloid layer for various purposes such as prevention of irradiation or halation. May be contained. 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 suitable dispersion method and added to the water-penetrating colloid layer.

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

Various color couplers can be used in the light-sensitive material using the silver halide photographic emulsion produced in the present invention, and specific examples thereof are described in Research Disclosure (RD) No. 17643, VII-CG. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and JP-B-58-10739.
British Patent Nos. 1,425,020 and 1,476,7
No. 60 is preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable. For example, US Pat. Nos. 4,310,619 and 4,351,8
No. 97, EP 73,636, U.S. Pat.
No. 61,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630
No. 4,540,654 are preferred.
Cyan couplers include phenolic and naphthol couplers, for example, US Pat. No. 4,052,
No. 212, No. 4,146,396, No. 4,22
No. 8,233, No. 4,296,200, No. 2,3
No. 69,929, No. 2,801,171, No. 2,
No. 772, 162, No. 2,895,826, No. 3,772,002, No. 3,758,309, No. 4,334,011, No. 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 No. 161 626
Those described in No. A are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in, for example, Research Disclosure No. No. 17643, Section VII-G, U.S. Pat.
No. 63,670, JP-B-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 a coloring dye has an appropriate diffusibility include, for example, US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,57.
No. 0 and West German Patent (Publication) No. 3,234,533 are preferred.

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

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing a development inhibitor is described in Research Disclosure No. 17643 VII
Patents described in section -F, JP-A-57-151944
No., No. 57-154234, No. 60-184248
And those described in U.S. Pat. No. 4,248,962 are preferred. Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No.
Nos. 097,140 and 2,131,188, and JP-A-59-157638 and JP-A-59-170840 are preferred.

Other couplers which can be used in a light-sensitive material using the silver halide photographic emulsion produced in the present invention include, for example, a competitive coupler described in US Pat. No. 4,130,427 and US Pat. 4,283,472
No. 4,338,393 and No. 4,310,61
No. 8, etc .;
No. 50, DIR redox compounds or DIR coupler releasing couplers described in JP-A-50-24252,
Couplers that release dyes that recolor after release as described in EP 173302A, Research Disclosure No. 11449, 24241, JP-A-61-201
247 and the like, and the ligand releasing couplers described in U.S. 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 solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,0
No. 27, etc. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, 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 (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tri-2-ethylhexyl phosphate) Dodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di-2
-Ethylhexyl phenyl phosphate), benzoates (eg, 2-ethylhexyl benzoate,
Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenols (eg, iso- Stearyl alcohol,
2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl)
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate) aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octyl aniline), hydrocarbons (eg, 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. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

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

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

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating and extrusion coating can be used. U.S. Pat.
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 photosensitive materials and heat developable color photosensitive materials. it can. Research Disclosure, No. 17123
(July 1978), or by utilizing a three-color coupler mixture as described in U.S. Pat. No. 4,126,46.
The present invention can be applied to black-and-white photographic materials such as those for X-rays by utilizing a black-colored coupler described in US Pat. No. 1,102,136 and British Patent No. 2,102,136. Stencil film 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 microfilms, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials. .

When the silver halide photographic emulsion produced in the present invention is applied to a color diffusion transfer photographic method, a peeling (peel apartment) type or JP-B-46-16356,
JP-A-48-33697, JP-A-50-13040 and British Patent No. 1,330,524 make it possible to increase the rigidity of a film unit that does not require peeling. The use of a polymeric acid layer protected by a neutralization timing layer in any of the above formats is advantageous for widening the processing temperature tolerance. When used in color diffusion transfer photography, it may be used by adding it to any layer in the light-sensitive material, or may be used as a developing solution component enclosed 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-filled lamps, mercury lamps, fluorescent lamps, and strobe or metal-burning flash bulbs are common. Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD) or a micro-shutter array using lanthanum-doped lead zirconate titanate (PLZT) or the like has a linear or planar shape. Exposure means combining the above light sources can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used for the development of the photosensitive material is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent,
A p-phenylenediamine compound is preferably used,
As representative examples, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonic acid And the like. These diamines are generally more stable in a salt than in a free state, and are preferably used.

The color developing solution includes a pH buffer such as an alkali metal carbonate, borate or phosphate, bromide,
It generally contains a development inhibitor or an antifoggant such as iodide, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, preservatives such as hydroxylamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dyes Forming couplers, competing couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity enhancers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonates Chelating agents such as carboxylic acids, West German Patent Application (OLS) No. 2,622,950
The antioxidants described above may be added to the color developer.

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

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process,
It may be performed individually. In order to further speed up the processing,
After the bleaching process, a processing method of performing a bleach-fixing process may be used. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids,
Quinones, nitrones and the like are used. Representative bleaches include ferricyanide; dichromate; iron (III
) Or organic complex salts of cobalt (III) such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid or citric acid, tartaric acid, malic acid, etc. Complex salts of organic acids; persulfate; manganate; nitrosophenol, and the like can be used.
Of these, iron (III) ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid (III) and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Further, the iron (III) complex salt of ethylenediaminetetraacetate is particularly useful in an independent bleaching solution and a single-bath bleach-fixing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleaching accelerators are described in the following specifications: U.S. Pat. No. 3,893,858, West German Patents 1,290,812 and 2,059,988, No.53-32736, No.53-57831, No.3
No. 7-418, No. 53-65832, No. 53-726
No. 23, No. 53-95630, No. 53-95731
No. 53-104232, No. 53-124424
No., 53-141623, 53-28426,
Research Disclosure, No. 17129 (1
A compound having a mercapto group or a disulfide group described in, for example, JP-A-50-140129;
-8506, JP-A-52-20832 and 53-3
No. 2735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, iodides described in JP-A-58-16235; West German Patent 966,410; Polyethylene oxides described in JP-A-2,748,430; polyamine compounds described in JP-B-45-8836; and JP-A-49-4243.
No. 4, No. 49-59644, No. 53-94927,
Compounds and iodides described in JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940;
Bromide ions can also be used. Among them, a compound having a mercapto group or a disulfide group is preferred from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,893,858.
No., West German Patent No. 1,290,812, JP-A-53-9
The compounds described in No. 5630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the sensitizer. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide, and thiosulfates are generally used. As a preservative for the bleach-fixing solution or the fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

After the bleach-fixing process or the fixing process, a washing process and a stabilizing process are usually performed. In the washing process and stabilization process, to prevent sedimentation and save water,
Various known compounds may be added. For example, in order to prevent precipitation, inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, water softener such as organic phosphoric acid,
Insecticides and antibacterial agents to prevent the generation of various bacteria, algae and mold, metal salts such as magnesium salts, aluminum salts and bismuth salts, or surfactants to prevent drying load and unevenness, and various Hardening agents and the like can be added as needed. Or, West, Phot. Sci. Eng., Photographic Science and Engineering, Vol. 6, 344
(1965) and the like. In particular, the addition of a chelating agent or an anti-binder is effective.

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

It is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate and the like as a membrane pH adjuster after the treatment. In addition, in the case of a color sensitizer for photography, a step (washing-stabilization) usually performed after fixing can be replaced with the above-mentioned stabilizing step and washing step (water saving processing). On this occasion,
When the amount of the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed. The washing and stabilization processing time is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, depending on the type of the photographic 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 speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,592, 3,342,599,
Research Disclosure, No. 14850 and no. 15159. Schiff base compound, N
o. 13924, a metal complex described in U.S. Pat. No. 3,719,492, JP-A-53-1
Including the urethane compound described in 35628,
JP-A Nos. 56-6235, 56-16133, 5
Nos. 6-59232, 56-67842, 56-8
Nos. 3734, 56-83735, 56-8373
No. 6, No. 56-89735, No. 56-81837,
No. 56-54430, No. 56-106241, No. 5
Nos. 6-107236, 57-97531 and 5
Examples thereof include precursors of various salt types described in JP-A-7-83565. The silver halide color light-sensitive material may contain various 1-phenyl-3-pyrazolidones as needed for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339 and JP-A-5-64339.
7-144547, 57-21111, 58
-50532, 58-50536, 58-50
No. 533, No. 58-50534, No. 58-50535
And No. 58-115438.

Various processing solutions are used at 10 to 50 ° C. A temperature of 33 ° C. to 38 ° C. is standard, but higher temperatures can accelerate the processing and shorten the processing time, and lower temperatures can achieve higher image quality and improved processing solution stability. it can. Also, for saving silver of the photosensitive material, West German Patent No. 2,226,770 or US Pat.
Processing using cobalt intensification or hydrogen peroxide intensification described in US Pat. No. 4,499 may be performed. Heaters, temperature sensors, liquid level sensors,
A circulation pump, a filter, a floating pig, a squeegee, and the like may be provided. In the case of continuous processing, a certain finish can be obtained by using a replenisher for each processing liquid to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction and the like. When the light-sensitive material is color paper, it can be bleach-fixed very generally, and when it is a color photographic material for photography, if necessary.

[0063]

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

After completion of the particle formation, the mixture was desalted and washed with a usual flocculation method, and then gelatin and water were added. The obtained silver bromide emulsion is a monodispersed cubic emulsion having a side length of 0.5 μm. The concentrations of molybdenum and tungsten were determined by the atomic absorption method for the prepared emulsion and the supernatant aqueous solution obtained by centrifuging the emulsion. From the difference, the amounts of molybdenum and tungsten incorporated in the particles were determined. As a result, it was found that about 20% of the added tungsten or molybdenum was incorporated in the particles. This emulsion was added with gelatin and sodium dodecylbenzenesulfonate, and gelatin, on a triacetyl cellulose film support having an undercoat layer,
Polymethyl methacrylate particles, 2,4-dichloro-6
Coated by extrusion with a protective layer containing -hydroxy-s-triazine sodium salt.

The samples were exposed to sensitometric exposure (1 second and 10 ^-3 seconds) via an optical wedge,
After developing with MAA-1 developer having the following formulation at 20 ° C. for 10 minutes, the solution 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 reciprocal of the exposure required to obtain an optical density of fog + 0.1. The gradation was determined by a gradient from the optical density of fog + 0.1 to the optical density of fog + 1.1 in the characteristic curve. That is, the optical density difference 1.0 was obtained by dividing the relative exposure amount giving an optical density of fog +0.1 from the relative exposure amount giving an optical density of fog +1.1. Here, the sensitivity and the gradation were expressed by setting the value of the emulsion in which no compound was added to 100.

[0066]

[Table 1]

Comparative compound A: Ammonium hexachloride iridate (III) 〃 B: Potassium hexabromide rhodium (III) 〃 C: Potassium ruthenium hexacyanate (II)

MAA-1 developer Metol 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g KBr 1.0 g Add water and add 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 illuminance exposure and high illuminance exposure. In particular, it can be seen that the effect in the high illuminance exposure is great.

Example 2 To the silver bromide emulsion prepared in Example 1 was added 3.9 × 10 ^-5 mol of sodium thiosulfate per mol of silver,
The mixture was heated for a minute for chemical ripening. Then, gelatin, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and sodium dodecylbenzenesulfonate were added, and gelatin, polymethyl methacrylate particles, 2,2 on a triacetyl cellulose film support having an undercoat layer. Coated by extrusion with a protective layer containing sodium 4-dichloro-6-hydroxy-s-triazine.

These samples were exposed and developed for sensitometry in the same manner as in Example 1. Here, the values for the sensitivity and the gradation were set to 100 in the same manner as in Example 1 for the emulsion to which the metal complex was not added.

[0072]

[Table 2]

As can be seen from Table 2, the silver halide emulsion into which the metal complex of the present invention was introduced exhibited high sensitivity and high gradation without depending on the exposure illuminance, and a great effect was obtained particularly in the high illuminance exposure.

Example 3 The temperature of the emulsion prepared in Example 1 was raised to 56 ° C., and sodium thiosulfate (6 × 10 ⁻⁶ mol / mol Ag) and chloroauric acid (8
(× 10 ⁻⁶ mol / mol Ag) and potassium thiocyanate (8 × 10 ⁻⁴ mol / mol Ag), and the mixture was chemically sensitized for 60 minutes. Then, gelatin, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetraazaindene and sodium dodecylbenzenesulfonate were added to form a triacetylcellulose film support having an undercoat layer,
Coating was performed by an extrusion method together with a protective layer containing gelatin, polymethyl methacrylate particles, and sodium 2,4-dichloro-6-hydroxy-s-triazine salt.

These samples were exposed and developed for sensitometry in the same manner as in Example 1. Here, the values for the sensitivity and the gradation were set to 100 in the same manner as in Example 1 for the emulsion to which the metal complex was not added.

[0076]

[Table 3]

From Table 3, it can be seen that the silver halide emulsion into which the metal complex of the present invention has been introduced has high sensitivity and high gradation without depending on the exposure illuminance even when used together with gold-sulfur sensitization. It can be seen that the effect can be obtained.

Example 4 An aqueous solution of silver nitrate (5.0 g of AgNO ₃ ) and an aqueous solution of sodium chloride (1.0 g) were added to 850 ml of an aqueous solution of pH 5.0 containing sodium chloride (4.5 g) and 25 g of gelatin kept at 50 ° C. while stirring. 7g) was added simultaneously at a constant flow rate over 10 minutes. Then, an aqueous silver nitrate solution (AgNO ₃
119.8 g), aqueous sodium chloride solution (41.1 g)
An 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 particle formation, the mixture was desalted and washed with ordinary flocculation, and then gelatin and water were added. The obtained silver chloride emulsion is a monodisperse cubic emulsion having a side length of 0.5 μm.

In the same manner as in Example 2, after coating on the support and exposure, 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 concentration was measured.
Here, the sensitivity and the gradation were expressed assuming that the value of the emulsion in which the metal complex was not added was 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 apparent from Table 4, high sensitivity and high gradation were achieved at both low illuminance and high illuminance when the metal complex of the present invention was introduced even in the silver chloride emulsion. In particular, the effect in high-illuminance exposure was remarkable.

Example 5 Ammonium nitrate (125 g) kept at 60 ° C.
Near (31.3 g), potassium bromide (51 g) and gelatin
While stirring into 25 liters of an aqueous solution containing 500 g of
AgNO3 aqueous solution (AgNO_Three4408 g) and potassium bromide
Aqueous solution (3088g) simultaneously over 50 minutes
did. Then, an aqueous solution of silver nitrate (AgNO _Three4492
g), an aqueous potassium bromide solution (3150 g) for 50 minutes
At the same time. Saturate silver potential during grain formation
It was kept at -40 mV with respect to the Japanese calomel electrode.

After completion of the particle formation, the resultant was desalted and washed with a usual flocculation method, and then gelatin and water were added. The obtained silver bromide emulsion is a monodispersed octahedral emulsion having a side length of 0.85 μm.

This emulsion was divided into small portions, and the compounds shown in Table 5 were added thereto and subjected to chemical ripening at 60 ° C. for 60 minutes. Then, a 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 dodecylbenzenesulfonate

Hardening agent: 1,2-bis (vinylsulfonylacetylamino) ethane

A preservative: phenoxyethanol was added, and the mixture was extruded onto a triacetyl cellulose film support having an undercoat layer together with a gelatin protective layer containing polymethyl methacrylate fine particles. Sensitometric exposure of these samples (1 sec and 10 ^-3 sec)
And the following color development processing was performed. The concentration of the treated sample was measured with a green filter. The relative sensitivity is
It was represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog + 0.1. The gradation is represented by the fog of the characteristic curve +0.
The optical density was determined from the optical density of No. 1 and the optical density of fog +1.1. That is, the optical density difference of 1.0 is changed to fog +
Fog +0.
It was determined by dividing by the relative exposure amount giving an optical density of 1. Here, the sensitivity and the gradation were expressed by setting the value of the emulsion in which no compound was added to 100.

[0092]

[Table 5]

The developing process used here was carried out under the following conditions.
C. was performed. 1. Color development 2 minutes 45 seconds Bleaching 6 minutes 30 seconds 3. Rinse 3 minutes and 15 seconds 4. Fixed arrival 6 minutes 30 seconds 5. Rinse 3 minutes 15 seconds 6. Stability 3 minutes 15 seconds The composition of the processing solution used in each step is as follows.

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

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

Fixer Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 g Sodium bisulfite 4.6 g Add water and add 1 liter

Stabilizer Formalin 8.0 ml Add water and add 1 liter

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

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

After completion of the particle formation, the mixture was desalted and washed with water by a usual flocculation method, and then gelatin and water were added. The obtained silver bromide emulsion is a monodispersed cubic emulsion having a side length of about 0.84 μm.

This emulsion was subdivided 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 subjected to chemical sensitization 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 concentration of the treated sample was measured with a green filter. The relative sensitivity was represented by the reciprocal of the exposure required to obtain an optical density of fog + 0.1. The gradation was determined by a gradient from the optical density of fog + 0.1 to the optical density of fog + 1.1 in the characteristic curve. That is, the optical density difference 1.0 was obtained by dividing the relative exposure amount giving an optical density of fog +0.1 from the relative exposure amount giving an optical density of fog +1.1. Here, the sensitivity and the gradation were expressed by setting the value of the emulsion in which no compound was added to 100.

[0102]

[Table 6]

Table 6 shows that the silver bromide cubic emulsion also
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 particularly large in high illuminance exposure. This indicates that the effect of adding the metal complex of the present invention does not depend on the crystal habit of the emulsion. Furthermore, it was found that the effects of the present invention were not impaired even when the metal complex of the present invention and a noble metal sensitizer were 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.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/015 G03C 1/09

Claims (1)

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