JP2847455B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material. In particular, the present invention provides a high-sensitivity halogenated halide with improved spectral sensitivity, improved high-intensity reciprocity failure, high contrast, high sensitivity in intrinsic absorption, and low intrinsic desensitization by a spectral sensitizing dye. The present invention relates to a photographic material using a silver emulsion.

[0002]

2. Description of the Related Art A technique (doping technique) of including a substance other than silver or halide ions (referred to as a dopant) in a silver halide crystal has been well known for a long time.
In particular, many studies have been made on the doping technique of transition metals (groups 3 to 12 of the periodic table) for the purpose of modifying silver halide emulsions. For example, Trivelli and Smith (Tr
U.S. Pat. No. 2,448,060 to Ivelli and Smith) describes the formula R ₂ MX ₆ , wherein R is a hydrogen, alkali metal or ammonium group, M is a trivalent transition metal of palladium or platinum, and X is Is a halogen atom)
At any stage of preparing silver halide-i.e., before or during precipitation of silver halide, or before or during first ripening (physical ripening), or second ripening. It is disclosed that a silver halide emulsion can be sensitized by adding it before (during chemical ripening) or during ripening.

[0003] There is a remarkable difference in the photographic effect of a transition metal compound in a silver halide emulsion between the case where a transition metal compound is added during the formation of silver halide grains and the case where it is added after the precipitation of silver halide grains. It has been known. In the former case, it is generally accepted that the transition metal penetrates into the silver halide grains as a dopant, effectively altering photographic performance despite its very small amount. When the transition metal is added after the formation of the silver halide grains is completed, the transition metal is adsorbed on the grain surface, but is often unable to approach the grains due to the interaction with the protective colloid. Add transition metal after particle formation,
In order to obtain the same effect as when a transition metal is incorporated as a dopant inside a silver halide grain, it is necessary to add a higher concentration of the transition metal. That is, it is generally recognized that a photographic effect is difficult to obtain when a transition metal is added during chemical sensitization, and the transition metal has been added during the formation of silver halide grains and used as a dopant. Regarding the technical difference between metal doping by adding a metal compound during formation of silver halide grains and metal sensitizer by adding a metal compound to an emulsion after formation of silver halide grains, Research Disclosure ( Research Disclosure, Vol. 176, December 1978
Item 17643, issued monthly, describes transition metal compounds added during grain precipitation in Chapter IA, and Chapter IIIA describes transition metal compounds introduced during chemical sensitization.

[0004] US Pat. No. 3,790,390 discloses that
Simple salts of metals of the 4th Periodic Table of the Periodic Table of the Elements, such as iron, cobalt, nickel, etc. and hexacoordinate complexes containing cyano ligands, simple salts of ruthenium, rhodium, palladium, osmium, iridium or halide ligands only The use of a six-coordination complex is disclosed. This describes a silver halide emulsion containing a six-coordinate cyano complex of iron (II), iron (III), and cobalt (III).

[0005] US Pat. No. 4,126,472 discloses that a silver halide emulsion is ripened in the presence of 10 ^-6 to 10 ^-4 mol of a water-soluble iridium salt per mol of silver halide, and iridium is doped on the surface of the grain or grains are doped. It is disclosed for use as a surface modifier. However, here 6
There is no description of the coordination cyano complex.

[0006] EP 0 242 190 describes that
A silver halide emulsion having silver halide grains formed in the presence of one or more complex compounds of trivalent rhodium having 3, 4, 5 or 6 cyanide ligands has high illuminance failure. It is disclosed to decrease.

US Pat. No. 3,690,888 discloses a method for producing silver halide containing a polyvalent metal ion, which comprises a step of producing silver halide in the presence of a protective colloid composed mainly of an acrylic polymer. ing.
Among these, bismuth, iridium, lead and / or osmium ions are specifically mentioned as polyvalent metal ions, but there is no description about a six-coordinated cyano complex.

[0008] These disclosures do not clearly show that the ligand is incorporated into the particles together with the transition metal, but also specify the ligand of the transition metal complex compound and its effect. Not.

[0009] On the other hand, European Patents 0336425 and 03
36426, JP-A-2-20853, JP-A-2-20853;
No. 20,854, each publication discloses that in the presence of a six-coordinate rhenium, ruthenium, osmium and iridium metal complex having at least four cyanide ligands, the sensitivity and the gradation stability over time are improved, and the low light failure is improved. Silver halide emulsions are described. In addition, European Patent 033
No. 6427, JP-A-2-20852 discloses that sensitivity is controlled by a hexacoordinate vanadium, chromium, manganese, iron, ruthenium, osmium, rhenium and iridium metal complex containing a nitrosyl or thionitrosyl ligand, Emulsions with improved low light reciprocity failure are disclosed. Also, European Patent 0336689,
JP-A-2-20855 discloses that the sensitivity of a ligand of a six-coordinate rhenium complex is controlled by a metal complex which is a combination of halogen, nitrosyl, thionitrosyl, cyan, water, and thiacian, and that low-illuminance reciprocity failure occurs. Are disclosed. Further, JP-A-3-118535
The publication discloses a transition metal complex in which one ligand of a six-coordinate metal complex is carbonyl, and the publication 3-118536 discloses a transition metal complex in which two ligands of a six-coordinate metal complex are oxygen. It is disclosed that the emulsion contained therein is effective for photographic performance.

In these disclosed examples, the six-coordinate transition metal complex is formed from seven vacancies from which one silver ion in the silver halide crystal structure and six halogen ions adjacent thereto are removed. It has been recognized that it is contained in space, which is different from the conventional general view that the transition metal is incorporated into the silver halide grains as a single ion or atom.

However, in these disclosed examples, ordinary gelatin is used as a protective colloid in forming silver halide grains doped with a metal complex. For the interaction between metal and gelatin, see T. James James, Theory of Photographic Process, 4th Edition, Macmillan, Inc. (TH
James, "The Theory of the Photographic Process" 4th
ed. Macmillan) in Chapter 2 (pp. 71-72). It has been shown that noble metals such as gold and platinum, iridium and other heavy metals interact with gelatin to form complex salts and reduce metals. Therefore, conventional transition metal complex compound doping techniques cannot sufficiently deal with unexpected effects such as oxidation or reduction of transition metal due to interaction between the transition metal complex and gelatin, exchange of ligands of the transition metal complex, and decomposition. Could not be controlled.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to minimize the interaction between a gelatin and a transition metal complex when doping a silver halide emulsion with a transition metal complex and to control the transition metal complex. The purpose of this is to maximize the effect obtained by doping the transition metal complex.

[0013]

The object of the present invention is to provide (1) a photographic material having a silver halide emulsion layer on a support, wherein the silver halide emulsion is prepared in the presence of a six- coordinate cyano complex. in some or all of the nucleation and / or crystal growth is performed, thereby saw including a hexacoordinated cyano complexes in the crystal lattice, further 10 g / Ag mole gelatin present
Under a synthetic polymer compound with protective colloid properties
Process from nucleation to chemical sensitization in the presence of
After finishing the feeling, use gelatin as a binder at 30 g / silver
The silver halide photographic material, wherein the silver halide emulsion obtained by adding more Le; (2) Engineering from the nucleus type formed gelatin absence to chemical sensitization
Providing the silver halide photographic material according to (1) above, and (3) supplying fine silver halide grains prepared in the presence of a synthetic polymer compound having protective colloidal properties. Part or all of the nucleation and / or crystal growth of the silver halide emulsion has been achieved by the silver halide photographic material according to (1) or (2).

The photographic material described above minimizes unexpected adverse effects on photographic performance due to oxidation or reduction of a transition metal, ligand exchange, decomposition, etc. caused by the interaction of hexacoordinate cyano complex with gelatin. The effect on the photographic performance of the silver halide doping of the six-coordinate cyano complex ion could be maximized.

Hereinafter, the present invention will be described in more detail. The six-coordinate cyano complex salt used in the present invention is a salt containing a six-coordinate transition metal complex ion satisfying the following (I). In the formula (I) [M (CN) ₆ ] ^{n -where} , M is the fifth, sixth, seventh or eighth group of the fourth, fifth and sixth periods of the Periodic Table of the Elements. A transition metal selected from Group 9, Group 9 and Group 10, preferably iron, cobalt, ruthenium, rhenium, rhodium,
Osmium and iridium; n is 3 or 4.

Since the hexacoordinate metal complex salt dissociates when introduced into, for example, an aqueous medium used for forming silver halide grains, the counter cation has little importance. However, ammonium and alkali metal counter cations are known to be well suited for silver halide precipitation operations and are particularly suitable as counter cations of six-coordinate transition metal complex salts that meet the requirements of the present invention.

The above six-coordinate cyano complex ion is incorporated into silver halide grain crystals. That is, the hexacoordinate cyano complex ion is a space formed from seven vacancies obtained by removing one silver ion and six halogen ions adjacent to the silver ion inside the crystal structure (seven vacancy ions). To be housed. Since these seven vacancy ions show a net charge of -5, an anion complex such as a six-coordinate cyano complex ion can be easily incorporated into the crystal lattice, and a six-coordinate transition metal complex can be obtained. Can be expected to depend on the magnitude of the difference between the charge of the introduced complex and the charge of the seven vacancy ions.

In the six-coordinate cyano complex salt, the central transition metal ion can occupy the position of silver ion, and six cyano ions can occupy the position of six halogen ions adjacent to the silver ion substituted. In addition, it is spatially similar to seven vacancy ions. Also, in terms of atomic size, silver ions are much smaller than bromide ions, silver bromide crystals can accommodate iodide ions larger than bromide ions, and cyano ligands of transition metal complexes From the fact that the covalent bond between the metal and the central transition metal reduces the bond distance and the size of the entire transition metal complex, the six-coordinate cyano complex salt has seven vacancies inside the silver halide crystal. It can be understood that the ions are substituted into the terminal point ions and incorporated into the silver halide crystal.

The hexacoordinate cyano complex salt satisfying the requirements of the present invention can be contained in silver halide grains at the same concentration per mole of silver as used conventionally in doping transition metals. . In this connection, a very wide range of concentrations is known, see JP-A-51-10712.
No. 3,867,676 and US Pat. No. 369,676 from the low concentration of 10 ⁻¹⁰ mol per mol of silver disclosed in US Pat.
No. 0891, 10 per mole of silver disclosed in each specification.
Used in the high concentration range of ^-3 molar. The effective concentration will vary greatly depending on the halide content of the grains, the selected transition metal, its oxidation state and the desired photographic effect, but the concentration of the six-coordinate cyano complex will be from 10 ^-8 to 10 ^-3 mole per mole of silver. Is more preferred.

The doping amount and doping ratio of the hexacoordinate cyano complex salt in the silver halide grains were determined by atomic absorption spectrometry, ICP method (Indus
ctively Coupled Plasma Spectrometry and ICPMS (Inductivel Plasma Spectrometry)
y Coupled Plasma Mass Spectrometry: Inductively coupled plasma mass spectrometry) or the like.

The six-coordinate cyano complex used in the present invention is:
It can be optionally added and contained during the preparation of silver halide grains, that is, during part or all of nucleation and / or crystal growth. In a more preferred embodiment, it is more preferable that the doping amount is large in the vicinity of the surface of the silver halide grains, but it is also preferable that the concentration is high in a region slightly deep from the surface of the silver halide grains. The pAg in the reaction solution when the hexacoordinate cyano complex salt is added during the preparation of silver halide grains is preferably 6 or more, more preferably 7 or more.

The six-coordinate cyano complex used in the present invention is preferably dissolved in water or a suitable solvent and added. To stabilize the solution, a method of adding an aqueous solution of a halide of an alkali metal (for example, KCl, NaCl, KBr, NaBr, or the like) can be used. If necessary, an alkali or the like may be added.

The six-coordinate cyano complex salt used in the present invention may be added directly to the reaction solution when forming silver halide grains,
It is preferable that the silver halide grains be contained in an aqueous halide solution for forming silver halide grains or in another solution to form grains. Furthermore, various addition methods can be combined.

Further, nucleation of silver halide grains and / or
Alternatively, when part or all of crystal growth is performed by supplying a silver halide emulsion containing fine silver halide grains prepared in the presence of a synthetic polymer compound having protective colloidal properties, The cyano complex salt may be supplied by being doped into fine silver halide grains, or may be supplied alone into the reaction vessel.

The concentration of hydrogen ions in the reaction solution when the hexacoordinate cyano complex salt used in the present invention is added is not particularly limited, but pH is preferably 3 or more.

The six-coordinate cyano complex used in the present invention can be used alone or in combination of two or more. It can also be used in combination with other metal ions. Other metal ions are added as long as they can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, hexacoordinate complexes, and tetracoordinate complexes. it can.

As the high molecular compound having a protective colloid action on silver halide grains used in the present invention, the following compounds are used.

A. Polyacrylamide polymer Acrylamide homopolymer, U.S. Pat.
Patent No. 4 discloses a copolymer of polyacrylamide and imidized polyacrylamide, West German Patent 120
No. 2132, copolymer of acrylamide and methacrylamide, U.S. Pat. No. 3,284,207, partially aminated acrylamide polymer, JP-B-45-14031, U.S. Pat.
Nos. 3834 and 3746548, British Patent 78834
3. A substituted acrylamide polymer as described in each of the specifications.

B. Amino polymer US Pat. Nos. 3,345,346, 3,706,504, 4,
No. 350759, West German Patent 2,138,872, the aminopolymers described in GB 1,413,125.
And polymers having a quaternary amine described in US Pat. No. 3,425,836, a polymer having an amino group and a carboxyl group described in US Pat. No. 3,511,818, and a polymer shown in US Pat. No. 3,832,185.

C. Polymers having thioether groups US Pat. Nos. 3,615,624, 3,860,428 and 3,
No. 706564 A polymer having a thioether group shown in each specification.

D. Polyvinyl alcohol Homopolymer of vinyl alcohol, US Patent 30007
No. 41, an organic acid monoester of polyvinyl alcohol, a maleic acid ester described in US Pat. No. 3,236,653, and a copolymer of polyvinyl alcohol and polyvinyl pyrrolidone described in US Pat. No. 3,479,189.

E. Acrylic acid polymer Acrylic acid homopolymer, US Pat. No. 3,832,185,
U.S. Pat. No. 4,137,273 Acrylic ester polymer having an amino group described in each specification, U.S. Pat.
Halogenated acrylate polymer shown in No. 1 and cyanoalkyl acrylate shown in U.S. Pat. No. 4,120,727.

F. Polymer having hydroxyquinoline A polymer having hydroxyquinoline described in US Pat. Nos. 4,030,929 and 4,152,161. G. FIG. Derivatives of cellulose and starch British Patent Nos. 542704 and 551659, U.S. Pat. Nos. 2,127,573, 2,231,086, and 23220
No. 85 Derivatives of cellulose or starch shown in each specification.

H. Acetal US Patent Nos. 2,358,836, 3,0038,879, and 2,
No. 828204 and British Patent No. 771155.

I. Polyvinylpyrrolidone Homopolymer of vinylpyrrolidone, French patent 203
No. 1396, a copolymer of acrolein and pyrrolidone.

J. Polystyrene A polystyrylamine polymer described in U.S. Pat. No. 4,315,071 and a halogenated styrene polymer described in U.S. Pat. No. 3,861,918.

K. Imidazole polymer JP-B Nos. 43-7561, 47-25374, 5
Nos. 2-16365, German Patent 201,095
And polymers having a vinylimidazole group described in the specifications of JP-A-2012970 and JP-A-2012970.

L. Others Azaindene group-containing vinyl polymer described in JP-A-59-8604, polyalkylene oxide derivative described in U.S. Pat. No. 2,976,150, polyvinylamine imide polymer described in U.S. Pat. No. 4,022,623, U.S. Pat. No., 408
No. 9688, U.S. Pat.
No. 84456, polyvinyl pyridine having an imidazole group described in U.S. Pat. No. 3,520,857, a vinyl polymer having a triazole group shown in Japanese Patent Publication No. 60-658, Japanese Journal of Photography, Vol. 29 No. 1, p. 18, polyvinyl-2-methylimidazole and acrylamide-imidazole copolymers, and water-soluble polyalkyleneaminotriazoles shown in Zeitschrift-Visenshaftrich Photography, Vol. 45, p. 43 (1950). No.

The amount of the synthetic polymer compound having a protective colloid of the present invention to be used is not particularly limited, but is preferably 150 g or less, more preferably 80 g or less, further preferably 20 g or less per mol of silver halide. It is preferred that

In the present invention, part or all of the nucleation and / or crystal growth of silver halide grains is carried out in the presence of a synthetic polymer compound having protective colloid properties, and the gelatin content at that time is reduced. Preferably it is at most 10 g / mol of silver, more preferably it contains no gelatin.

After the nucleation of silver halide grains ,
Crystal growth, the content of a gelatin which definitive the process of washing and desalting ~ chemical sensitization Ri der 1 0 g / silver mole, and most preferably free of a gelatin at all. However, during the period from the end of chemical sensitization to immediately before coating, gelatin is used as a vehicle (binder) and 3 mol / mol of silver halide is used.
It is necessary to add 0 g or more, preferably 50 g or more. See RESEACH for available vehicles.
DISCLOSURE Volume 176 Item 1764
3 can be referred to. The temperature at the time of particle formation in the present invention is in the range of 10 ° C to 95 ° C, preferably in the range of 40 ° C to 80 ° C.

In the present invention, a part or all of the nucleation and / or crystal growth of the silver halide grains is performed by using fine silver halide grains prepared in the presence of a synthetic polymer compound having protective colloidal properties. It is preferably carried out by supplying a contained silver halide emulsion.
This technique is disclosed in Japanese Patent Application Laid-Open No. 1-183417,
Nos. 183644, 1-183645 and 2-43
Nos. 534, 2-43535 and 2-44335
No. 4,879,208 and European Patent 0
No. 408,752 discloses the technology.

The concentration of the synthetic polymer compound having protective colloidal properties to be used is not particularly limited, but is preferably 20% by weight or less, preferably 10% by weight, for an emulsion containing fine silver halide grains. %, More preferably 5% by weight or less.

The amount of the synthetic polymer compound having a protective colloid of the present invention to be used in the reaction solution to which the emulsion containing fine silver halide grains is supplied is not particularly limited. It is preferably 150 g or less per mole, more preferably 80 g or less, and further preferably 20 g or less.
The following is preferred. The gelatin content at that time is preferably at most 10 g / silver mole, and more preferably contains no gelatin.

Further , it contains fine silver halide grains.
The content of a gelatin which definitive the process of washing and desalting ~ chemical sensitization of the emulsion 1 0 g / silver mole or less it is favorable preferred, and more preferably contains no gelatin. However, during the period from the end of chemical sensitization to just before coating,
It is necessary to add gelatin as a vehicle (binder) in an amount of 30 g or more, preferably 50 g or more per mol of silver halide. For vehicles that can be used, see R
ESEACH DISCLOSURE 176 Volume I
The description of tem 17643 can be referred to.
The temperature at the time of particle formation in the present invention is in the range of 10 ° C to 95 ° C, preferably in the range of 40 ° C to 80 ° C. The temperature at which fine silver halide grains are formed is 40 ° C. or lower, preferably 35 ° C. or lower.

The grain size of the fine silver halide grains can be confirmed by placing the grains on a mesh and using a transmission electron microscope as it is. The magnification at this time is preferably 20,000 to 40,000. The size of the fine particles of the present invention is 0.0
It is 6 μm or less, preferably 0.03 μm or less, and more preferably 0.01 μm or less.

The emulsion obtained by the present invention has a silver halide composition of silver bromide, silver chloride, silver iodobromide, silver iodochloride,
Any of silver chlorobromide and silver iodochlorobromide may be used. The grain size of the silver halide grains of the present invention is not particularly limited, but is from 0.05 μm to 10 μm, preferably from 0.1 μm to 3 μm. The size of the silver halide grains of the present invention can be adjusted by controlling the temperature and pAg, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth.

Examples of frequently used silver halide solvents include thiocyanates, thioethers, and thioureas, and ammonia can be used in combination as long as no adverse effect is caused. For example, thiocyanates (U.S. Pat. Nos. 2,222,264 and 24,485)
No. 34, No. 3320069, etc.), thioether compounds (for example, US Pat.
No. 74628, No. 3704130, No. 4297439
No. 4,276,347), thione compounds (for example, JP-A-53-144319, JP-A-53-824).
08, 55-77737, and amine compounds (for example, JP-A-54-100717).

The shape of the silver halide grains according to the present invention may be a regular crystal form (normal crystal grains) such as hexahedron, octahedron, dodecahedron, tetrahedron, 24 tetrahedron, and 48-octahedron. Particles having irregular crystal forms such as spheres and potatoes, and particles of various shapes having one or more twin planes, particularly two or three parallel twin planes. May be hexagonal tabular grains and triangular tabular twin grains.

For the production of the silver halide emulsion used in the present invention, any method known so far can be used. That is, a silver salt aqueous solution and a halogen salt aqueous solution are added to a reaction vessel having an aqueous gelatin solution with efficient stirring. As a specific method, P. Glafkides
By Chemie et Phisique Photographique (Paul Montel
Publisher, 1967), Photographic Emulsi by GF Duffin
on Chemistry (The Focal Press, 1966), VL
Making and Coating Photographic by Zelikman et al
It can be prepared using a method described in Emulsion (The Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-mixing method, a combination thereof, and the like. Good. As one form of the simultaneous mixing method,
A method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can also be used. Also, British Patent 1535
No. 016, JP-B-48-36890, and JP-B2-52.
No. 4,364,445, US Pat. No. 4,424,445, Japanese Patent Application Laid-Open No. 55-158124, and the like. It is preferred that the growth be carried out quickly within a range not exceeding the critical supersaturation using the method of changing the concentration of the aqueous solution as described in (1). These methods are preferably used because they do not cause renucleation and the silver halide grains grow uniformly.

Further, in the present invention, emulsion grains having various structures can be used. So-called core / shell double-structured particles composed of the inside (core portion) and the outside (shell portion) of the particles, triple-structured particles as disclosed in JP-A-60-222844, and multilayers of more than that. Structural particles are used. When a structure is provided inside the emulsion grains, not only the above-described wrapping structure but also a grain having a so-called junction structure can be produced. These examples are disclosed in JP-A-59-133540 and JP-A-58-133540.
No. 108526, European Patent No. 199,290A2
Specification, JP-B-58-24772, JP-A-59-1
No. 6,254, each publication.

The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in halogen composition or has a core-shell structure.

In the case of a junction structure, a combination of silver halides is naturally possible, but a silver salt compound having a non-rock salt structure such as silver rhodanate and silver carbonate can be combined with silver halide to form a junction structure. Further, a non-silver salt compound such as PbO may be used as long as it can form a junction structure.

In the case of silver iodobromide particles having these structures, for example, in a core-shell type particle, even if the silver iodide content in the core portion is high and the silver iodide content in the shell portion is low, Conversely, grains having a low silver iodide content in the core portion and a high silver iodide content in the shell portion may be used. Similarly, particles having a bonding structure may be particles having a high silver iodide content in the host crystal and a relatively low silver iodide content in the bonding crystal, or vice versa. Also,
The boundary portions having different halogen compositions in the grains having these structures may be clear boundaries, or may be unclear boundaries due to the formation of a mixed crystal due to a composition difference. It may have a structural change.

The silver halide emulsion used in the present invention is EP
No. 0096727B1, EP-0064412B1 and the like, which impart roundness to the particles, or modify the surface as disclosed in DE-2306447C2 and JP-A-60-221320. Quality may be performed.

The silver halide emulsion used in the present invention is preferably a surface latent image type, but as disclosed in JP-A-59-133542, an internal latent image type is selected by selecting a developing solution or developing conditions. Emulsions can also be used.
Also, a shallow internal latent image type emulsion covered with a thin shell can be used depending on the purpose.

In the present invention, it is preferable to use silver halide grains having dislocation lines. The grains having dislocation lines are disclosed in U.S. Pat. No. 4,806,461.

The emulsion of the present invention is usually spectrally sensitized. Examples of the dye used for this include a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye,
And styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. As these dyes, any of nuclei usually used for cyanine dyes can be applied as basic heterocyclic nuclei. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a selenazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, a tellurazole nucleus, and the like; Fused nuclei: and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzotellurazole nucleus, and the like can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

As the merocyanine dye or composite merocyanine dye, any nucleus generally used for merocyanine dyes can be used as the nucleus having a ketomethylene structure. Particularly useful nuclei are pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-
Applying a 5-membered or 6-membered heterocyclic nucleus such as a dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, and a 2-thioselenazolidine-2,4-dione nucleus. Can be.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,977,229,
No. 3397060, No. 3522052, No. 3527
No. 641, No. 3617293, No. 3628964,
No. 3666480, No. 3672898, No. 3679
No. 428, No. 3703377, No. 3769301,
Nos. 3614609, 3837862, 4026
No. 707, British Patent Nos. 1344281 and 150780
No. 3, each specification, JP-B-43-4936, and JP-B-53-12
No. 375, JP-A-52-110618, JP-A-52-10
No. 9925, etc.

Furthermore, these sensitizing dyes are dyes which do not themselves exhibit spectral sensitizing action, or substances which do not substantially absorb visible light, and exhibit marked spectral sensitization when combined with sensitizing dyes. It may be used in combination with any compound known as a so-called supersensitizer exhibiting an increase. Representative examples of supersensitizers include bispyridinium salt compounds described in JP-A-59-142541, stilbene derivatives described in JP-B-59-188691, JP-B-49-46932 and the like. Water-soluble bromides such as potassium bromide and potassium iodide, water-soluble iodides, condensates of aromatic compounds and formaldehyde described in U.S. Patent No. 3,743,510 and the like, cadmium salts, azaindene compounds and the like No. The sensitizing dye is added after or before chemical ripening. For the silver halide grains of the present invention, it is most preferable that the sensitizing dye is added during or before chemical ripening (for example, during grain formation or physical ripening).

The silver halide emulsion of the present invention is usually chemically sensitized. As the chemical sensitization in the present invention, chalcogen sensitization such as sulfur sensitization, selenium sensitization, and tellurium sensitization, and noble metal sensitization and reduction sensitization are used alone or in combination.

In the sulfur sensitization, an unstable sulfur compound is used and is described by Chimie et Physique Photograph by P. Grafkides.
ique (Paul Momtel, 1987, 5th edition), Research
Unstable sulfur compounds described in Disclosure 307, 307105 and the like can be used. Specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, N-
Ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethyl rhodanine, 5-benzylidene-N-ethyl-) Rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg,
Known sulfur compounds such as dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (eg, cysteine), polythionates, elemental sulfur, and active gelatin can also be used.

In selenium sensitization, an unstable selenium compound is used, and JP-B-43-13489 and JP-B-44-157.
No. 48, JP-A-4-25832, JP-A-4-109240
Gazettes, Japanese Patent Application Nos. 3-53693 and 3-82929.
Unstable selenium compounds described in the specifications of the above publications can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenoacetamide, N, N-diethylphenylselenoamide), phosphine selenides (e.g., triphenylphosphine selenide, pentafluorophenyltriphenylphosphine selenide), selenophosphates (e.g., tri-p-tolylselenophosphate, Tri-n-butylselenophosphate), selenoketones (eg, selenobenzophenone), isoselenocyanates, selenocarboxylic acids,
Selenoesters and diacylselenides may be used. Furthermore, Japanese Patent Publication No. 46-4553 and 52-3
Non-labile selenium compounds described in 4492 publications and the like,
For example, selenous acid, potassium selenocyanide, selenazoles, selenides and the like can be used.

In tellurium sensitization, an unstable tellurium compound is used, and Canadian Patent 800958, British Patent 129
Nos. 5462 and 1396696, Japanese Patent Application No.
333819, 3-53693, 3-1315
Unstable tellurium compounds described in JP-A Nos. 98 and 4-129787 and the like can be used. Specifically, telluroureas (e.g., tetramethyltellurourea, N, N'-dimethylethylenetellurourea, N, N '
-Diphenylethylene tellurourea), phosphine tellurides (e.g., butyl-diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) telluride (For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), isotellurocyanates, Telluramides, tellurohydrazides, telluroesters (eg, butylhexyltelluroester), telluroketones (eg, telluroacetophenone), colloidal tellurium, (di) tellurides, and other tellurium compounds Potassium nitrosium telluride, tellurocarbonyl penta isethionate sodium salt) or the like may be used.

The noble metal sensitization is described in P. Grafkid
es, Chimie et Physique Photographique (Paul Momt
el company, 1987, 5th edition), Research Disclosure 3
Gold, platinum, and the like described in Vol.
Noble metal salts such as palladium and iridium can be used, and gold sensitization is particularly preferable. Specifically, in addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide, U.S. Patent Nos. 2642361, 5049484, and 50494
The gold compounds described in the specification of No. 85 can also be used.

Regarding reduction sensitization, see the aforementioned P. Grafkides.
Written by Chimie et Physique Photographique (Paul Momtel
Publishing Company, 1987, 5th edition), Research Disclosure Magazine 30
Known reducing compounds described in Vol. 7, No. 307105, etc. can be used. Specifically, aminoiminomethanesulfinic acid (also called thiourea dioxide), borane compound (for example, dimethylaminoborane), hydrazine compound (for example, hydrazine, p-tolylhydrazine), polyamine compound (for example, diethylenetriamine, triethylene Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas, and the like may be used. The reduction sensitization may be performed in an atmosphere having a high pH or an excess of silver ions (so-called silver ripening).

These chemical sensitizations may be used alone or in combination of two or more. When combined, a combination of chalcogen sensitization and gold sensitization is particularly preferable. Further, reduction sensitization is preferably performed at the time of forming silver halide grains.

The amount of the chalcogen sensitizer used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical sensitization, and the like, but is preferably 10 ^-8 to 10 per mol of silver halide.
^-2 mol, preferably about 10 ^{-7 to} 5 × 10 ^-3 mol is used.

The noble metal sensitizer used in the present invention is used in an amount of about 10 ^-7 to 10 ^-2 mol per mol of silver halide. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pAg is preferably 6 to 11, more preferably 7 to 10, the pH is preferably 4 to 10, and the temperature is 40 to 95 ° C. 45-85 ° C is preferred.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . Azoles, such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds, such as mercaptothiazoles, mercapto Benzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto having a water-soluble group such as a carboxyl group or a sulfone group Compounds; thioketo compounds such as oxazolinethione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); Thiosulfonic acids; benzenesulfinic acid; can be added to many compounds known as antifoggants or stabilizers, such as.

The timing of adding these antifoggants or stabilizers is usually performed after chemical sensitization, but can be more preferably selected during chemical ripening or before chemical ripening. .

The emulsion of the present invention has a single emulsion layer or two emulsion layers.
It can be used for a photographic light-sensitive material having an arbitrary layer constitution irrespective of whether it has more than one layer. The silver halide multilayer color photographic light-sensitive material using the emulsion of the present invention has a multi-layer structure in which emulsion layers containing a binder and silver halide grains are superposed for separately recording blue, green and red light. Each emulsion layer comprises at least two layers, a high-speed layer and a low-speed layer.

The silver halide emulsion of the present invention can be applied to a color light-sensitive material as described above. The light-sensitive material having one or more emulsion layers, other than the above, such as a light-sensitive material for X-rays and black-and-white The present invention can be similarly applied to a photosensitive material for photography, a photosensitive material for plate making, photographic paper, and the like.

Various additives of the silver halide emulsion of the present invention, for example, binder, chemical sensitizer, spectral sensitizer, stabilizer, gelatin hardener, surfactant, antistatic agent, polymer latex, matting agent There are no particular restrictions on the support, coating method, exposure method, development processing method and the like of a light-sensitive material using a color coupler, an ultraviolet absorber, an anti-fading agent, a dye and an emulsion thereof, for example, Research Disclosure Vol. Item 17643 (RD-17
643), same volume 187, item 18716 (RD-1
8716) and 225, Item 22534 (R
D-22534) can be referred to.

The descriptions of these research disclosures are shown in the following table.種類 Additive type RD17643 RD18716 RD22534 ──────── １ 1 Chemical sensitizer Page 23 648 Right column Page 24 2 Sensitivity enhancer Same as above 3 Spectral sensitization P. 23-24 p. 648 right column to p. 24-28 supersensitizer 649 p. Right column 4 Brightener p. 24 p. 5 Antifoggant p. 24-25 p. 649 p. Right column p. 24, p. 31 and stabilizer Reference Signs List 6 light absorbers, pages 25-26 page 649 right column to filter dye 650 page left column UV absorber 7 stain inhibitor 25 page right column 650 page left-right column 8 dye image stabilizer page 25 page 32 9 hard film Page 26 651 left column page 28 10 binder 26 page Same as above 11 plasticizer and lubricant page 27 65 Page right column 12 Coating aid, surface 26-27 Same as above Activator 13 Static inhibitor page 27 Same as above 14 Color coupler 25 25 649 31 ──────────────────

The color coupler used in the present invention preferably has a ballast group or has a diffusion resistance by being polymerized. A two-equivalent coupler substituted with a coupling-off group is more preferable than a four-equivalent coupler having a hydrogen atom at the coupling active position, since the amount of coated silver can be reduced. Further, a coupler in which a coloring dye has an appropriate diffusibility, a non-color coupler or a DIR coupler which releases a development inhibitor with a coupling reaction,
Alternatively, couplers that release a development accelerator can also be used.

As a yellow coupler usable in the present invention, an oil protect type acylacetamide coupler can be mentioned as a typical example. Typical examples thereof include an oxygen atom-eliminable yellow coupler and a nitrogen atom-eliminable yellow coupler. α-pivaloylacetanilide-based couplers are excellent in the fastness of color-forming dyes, especially in light fastness, while α-benzoylacetoanilide-based couplers can provide high color density.

Examples of the magenta coupler usable in the present invention include pyrazoloazole couplers such as oil-protected indazolone couplers and cyanoacetyl couplers, preferably 5-pyrazolone and pyrazolotriazoles. As the 5-pyrazolone-based coupler, a coupler in which the 3-position is substituted with an arylamino group or an amylamino group is preferable from the viewpoint of the hue and color density of the coloring dye.

The imidazo [1,2-b] pyrazoles described in US Pat. No. 4,500,630 are preferred from the viewpoints of low yellow sub-absorption of the coloring dye and light fastness.
Pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,540,650 are particularly preferred.

Cyan couplers usable in the present invention include oil-protected naphthol couplers and phenol couplers, and the naphthol couplers described in US Pat. No. 2,474,293, preferably US Pat. Nos. 4,052,212 and 4,146,396. , 42282
Representative examples thereof include an oxygen atom-eliminating double-equivalent naphthol coupler described in JP-A Nos. 33 and 4296200.

Japanese Patent Application Nos. 59-93605 and 59-26
Cyan couplers described in JP-A-4277 and JP-A-59-268135, in which a sulfonamide group, an amide group, etc. are substituted at the 5-position of naphthol, are also excellent in color image fastness and can be preferably used in the present invention. .

The granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such couplers are described in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570, and specific examples of magenta couplers, and in EP 96570 and West German Patent Publication 32.
No. 34533 describes specific examples of yellow, magenta or cyan couplers.

The present invention may include a coupler which releases a development inhibitor during development, a so-called DIR coupler. In combination with the present invention in a DIR coupler,
More preferred are a developer deactivating type represented by JP-A-57-151944; a timing type represented by U.S. Pat. No. 4,248,962 and JP-A-57-154234; The reaction types represented by 39653 are particularly preferable, and among them, particularly preferable ones are described in JP-A Nos. 57-151944 and 58-21793.
No. 2, Japanese Patent Application Nos. 59-75474 and 59-82214.
DIR couplers described in JP-A-59-82214 and JP-A-59-90438 and reaction type D described in Japanese Patent Application No. 59-39653.
It is an IR coupler.

In the light-sensitive material of the present invention, there can be used a compound which releases a nucleating agent or a development accelerator or a precursor thereof (hereinafter referred to as a "development accelerator") imagewise during development. Typical examples of such compounds are described in UK Patent Nos. 2097140 and 2131188, and couplers which release a development accelerator or the like by a coupling reaction with an oxidized aromatic primary amine developer. , That is, a DAR coupler.

Specific examples of the high boiling point organic solvent used for dispersing the color coupler include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate,
Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tridodecyl phosphate, etc.) Butoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexylpheninephosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecaneamide, N-tetradecylpyrrolidone, etc.), alcohols Or phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N,
N-dibutyl-2-butoxy-5-tert-octylaniline and the like, and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene and the like). In addition, as the auxiliary solvent, the boiling point is about 30 ℃ or more,
Preferably, an organic solvent having a temperature of 50 ° C. or more and about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

As the gelatin hardener, for example, active halogen compounds (2,4-dichloro-6-hydroxy-
1,3,5-triazine and its sodium salt, etc.)
And active vinyl compounds (such as 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane or a vinyl-based polymer having a vinylsulfonyl group in the side chain) are used to form hydrophilic colloids such as gelatin. It is preferable because it cures quickly and gives stable photographic properties. N-carbamoylpyridinium salts (1
-Morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate) also have fast and excellent curing rates.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is usually subjected to a washing treatment or a stabilization treatment after development, bleach-fixing or fixing. In the water washing step, two or more tanks are generally countercurrently washed to save water. As a typical stabilizing process, a multi-stage countercurrent stabilizing process as described in JP-A-57-8543 is exemplified instead of the washing step.

The color developing solution used in the development of the light-sensitive material of the present invention 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, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose.

When performing the inversion processing, usually,
Color development is performed after black-and-white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone,
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 color developing solution and the black and white developing solution
H is generally 9-12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. In addition, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both the bleaching and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5.
~ 8, but lower pH for faster processing
Can also be processed.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
As a useful bleaching accelerator, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,938,858 and West German Patent 129.
Compounds described in JP-A-08812 and JP-A-53-95630 are preferred. In addition, U.S. Pat.
The compounds described in the specification of JP-A-4 are also preferred. These bleaching accelerators may be added to the light-sensitive material.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal of the Society of Motion Pictur.
e and Television Engineers Vol. 64, p. 248-
253 (May 1955).

[0095]

The present invention will be described in detail with reference to the following examples.
The present invention is not limited to this.

[Example 1] "Emulsion A-1: Silver bromide octahedral emulsion using gelatin"
(Comparative Example) 36 g of gelatin and 0.25 g of potassium bromide were added to and dissolved in 866 cc of water, and a 0.083 M (mol / l) silver nitrate aqueous solution (solution 1) was stirred in a solution kept at 75 ° C. 36) and 36 cc of 0.088M aqueous potassium bromide solution (solution 2) were added in 10 minutes, followed by 176 cc of solution 1 and solution 2 in 7 minutes by the usual double jet method. After an additional 1.4 g of potassium bromide was added, a 0.82 M silver nitrate aqueous solution (solution 3) 1010 c
c was increased from a flow rate of 1.8 cc / min
At the same time, a 0.90 M aqueous potassium bromide solution (solution 4) was added with a silver potential of 0 mV (vs. a saturated calomel electrode).
Was added while controlling to keep at In addition, 0.
578 cc of a 51 M silver nitrate aqueous solution (solution 5)
578 cc of 1 M aqueous potassium bromide solution (Solution 6)
At a constant flow rate over a period of minutes. After completion of the addition, the temperature was lowered to 35 ° C., and soluble salts were removed by a normal sedimentation method.
Adjusted to 6.3. The obtained particles have a projected area diameter of 0.8 μm.
m of monodispersed silver bromide octahedral grains (coefficient of variation: 10%).

"Emulsion B-1: a silver bromide octahedral emulsion using a synthetic compound having protective colloid properties" (Comparative Example) A synthetic protective colloid represented by the following formula (1) in place of the gelatin of Emulsion A-1 Was formed in the same manner as in Emulsion A-1, except that 2 g was used.

[0098]

Embedded image

However, the sedimentation was spontaneous sedimentation, washed three times with water by the decantation method to remove soluble salts, and
Adjusted to 6.3. The obtained particles have a projected area diameter of 0.8 μm.
m of monodispersed silver bromide octahedral grains (coefficient of variation: 10%).

"Emulsions A-2 to A-5: octahedral silver bromide emulsion doped with hexacoordinate cyano complex using gelatin"
(Comparative Example) The following (2), (3), and
Except that (4) and (5) were dissolved at 5 × 10 ⁻⁴ M,
Emulsions obtained in exactly the same manner as Emulsion A-1, A-2, A
-3, A-4 and A-5 were prepared.

(2) K ₄ [Fe (CN) ₆ ]

(3) K ₃ [Fe (CN) ₆ ]

(4) K ₄ [Ru (CN) ₆ ]

(5) K ₃ [Ir (CN) ₆ ]

"Emulsion B-2 to B-5: octahedral silver bromide emulsion doped with a 6-coordinate cyano complex salt using a synthetic compound having protective colloid properties" (the present invention) Solution 6 of emulsion B-1 And (2), (3),
Except that (4) and (5) were dissolved at 5 × 10 ⁻⁴ M,
Emulsions obtained in exactly the same manner as Emulsion B-1, B-2, B
-3, B-4 and B-5 were prepared.

Next, A-1, B-1, A-2, A-3, A
-4, A-5, B-2, B-3, B-4 and B-5 were combined with 1.2 × 10 ⁻⁵ mol / mol silver sodium thiosulfate and 3.6 × 10 ^−6. It was optimally chemically sensitized with mol / mol silver potassium chloroaurate and 5.1 × 10 ⁻⁴ mol / mol silver potassium thiocyanate. 2g of these
/ M ² of silver. However, B-1, B-2, B
-3, B-4 and B-5 emulsions after completion of chemical sensitization
Gelatin was added as a coating binder.

The obtained coating samples were coated with coating samples A-1 and B-
1, A-2, A-3, A-4, A-5, B-2, B-
3, B-4 and B-5. Further, after the above-mentioned emulsion was subjected to the above-mentioned chemical sensitization, 2.5 × 10 ⁻⁴ mol / mol silver of a spectral sensitizing dye shown in the following (6) was added immediately before coating, and halogen was added at 40 ° C. for 20 minutes. It was adsorbed on silver halide particles.

[0108]

Embedded image

The above emulsion was coated in the same manner with a silver amount of ² g / m ² . The obtained coating samples were coated with coating samples A-1 ′ and B-
1 ', A-2', A-3 ', A-4', A-5 ', B-
2 ′, B-3 ′, B-4 ′ and B-5 ′.

The coated sample prepared as described above was subjected to 10 ^-3 with an Easy & G (EG & G) sensitometer.
After blue exposure for 2 seconds, development processing was performed. The developer is MA
A-1 developer was used at 20 ° C. for 10 minutes.

{MAA-1 Developer} ────────────────────────────── Methol 2.5 g L-ascorbic acid 10.0 g Nabox 35 g KBr 1.0 g H ₂ O 1 liter ────────────────────────────────────

The results obtained are shown in Table 1.

[0113]

Table 1-Emulsion Protection Dopant Relative Blue Tone Intrinsic desensitization width (* 3) Colloid sensitivity (* 1) (* 2) ΔlogE reference ────────────────────────────── ────── A-1 gelatin -100 1.5 -0.67 Comparative Example B-1 (1) -90 1.4 -0.65 Comparative Example A-2 Gelatin [Fe (CN) ₆ ] ^{4 -} 30 1.8 -0.35 Comparative example A-3 gelatin ^{_{[Fe (CN) 6] 3-}} 25 1.7 -0.37 Comparative example A-4 gelatin ^{_{[Ru (CN) 6] 4-}} 45 1. 9 -0.33 Comparative example A-5 gelatin ^{_{[Ir (CN) 6] 3-}} 50 1.8 -0.35 Comparative example B-2 (1) [Fe (CN) 6] 4- 130 2.0 - 0.23 The present invention B-3 (1) [Fe (CN) 6] 3- 125 1.9 -0.25 present invention B-4 (1) [Ru (CN) 6] 4- 135 2.1 - 0.22 pcs Invention B-5 (1) [Ir (CN) 6] 3- 125 2.0 -0.17 present invention ──────────────────────── ────────────

(* 1) Relative value of the reciprocal of the exposure amount that gives fog + density of 0.1 for samples A-1 to B-5 coated with spectral sensitizing dye blank. (* 2) Spectral sensitizing dye blank samples A-1 to B
-5 represents the slope of the straight line portion of the characteristic curve. (* 3) Spectral sensitizing dye blank coated samples A-1 to B
-5 and coating samples A-1 'to B containing the spectral sensitizing dye.
The logarithmic difference of the exposure amount E giving a fog + density of -5 '.

As is clear from Table 1, the emulsion in which gelatin and the dopant coexist has a significant adverse effect on the intrinsic sensitivity due to the interaction between gelatin and the transition metal complex.
A light-sensitive material using the emulsion of the present invention has high intrinsic sensitivity and high contrast at high illuminance, and remarkably improves intrinsic desensitization by a spectral sensitizing dye.

Example 2 "Emulsion C-1: Octahedral Emulsion Using Gelatin" (Comparative Example) In Emulsion A-1, 1% by weight of gelatin was added to Solution 2, Solution 4 and Solution 6; Solution 1, Solution 2, Solution 3, Solution 4, Solution 5 and Solution 6 are introduced into a mixer installed outside the reaction vessel, and a 1% by weight aqueous gelatin solution as Solution 7 is added to the above mixer. The emulsion was prepared in the same manner as in Emulsion A-1, except that a fine silver halide emulsion obtained by simultaneous introduction of the above was supplied into a reactor.

"Emulsion D-1: a silver bromide octahedral emulsion using a synthetic compound having a protective colloid property" (Comparative Example) A synthetic protective colloid represented by the following formula (7) instead of the gelatin of Emulsion C-1 In a reaction vessel, and solution 2,
It was prepared in the same manner as in Emulsion C-1, except that 0.1% by weight of Solution 4, Solution 6 and Solution 7 was used.

[0118]

Embedded image

However, the sedimentation was natural sedimentation, washed three times with water by a decantation method to remove soluble salts, and
Adjusted to 6.3.

"Emulsion C-2 to C-5: Silver bromide octahedral emulsion doped with 6-coordinate cyano complex using gelatin"
(Comparative Example) Solutions 6 of Emulsion C-1 were added with (2), (4),
Except that (8) and (9) were dissolved at 5 × 10 ⁻⁴ M,
Emulsion obtained exactly in the same manner as Emulsion C-1, C-2, C
-3, C-4 and C-5 were prepared.

(8) K ₃ [Co (CN) ₆ ]

(9) K ₄ [Re (CN) ₆ ]

"Emulsion D-2 to D-5: octahedral silver bromide emulsion doped with a hexacoordinate cyano complex using a synthetic compound having a protective colloid property" (the present invention) Solution 6 of emulsion D-1 And (2), (4),
Except that (8) and (9) were dissolved at 5 × 10 ⁻⁴ M,
Emulsions obtained in exactly the same manner as Emulsion D-1, D-2, D
-3, D-4 and D-5 were prepared.

Next, C-1, D-1, C-2, C-3, C
-4, C-5, D-2, D-3, D-4 and D-5 were combined with 1.2 × 10 ⁻⁵ mol / mol silver sodium thiosulfate and 3.6 × 10 ^−6. It was optimally chemically sensitized with mol / mol silver potassium chloroaurate and 5.1 × 10 ⁻⁴ mol / mol silver potassium thiocyanate. 2g of these
/ M ² of silver. However, D-1, D-2, D
-3, D-4 and D-5 emulsions after completion of chemical sensitization
Gelatin was added as a coating binder.

The obtained coating samples were coated with coating samples C-1 and D-
1, C-2, C-3, C-4, C-5, D-2, D-
3, D-4 and D-5. Further, after the above emulsion was subjected to the above chemical sensitization, 2.5 × 10 ⁻⁴ mol / mol silver of the spectral sensitizing dye shown in (6) was added immediately before coating,
It was adsorbed on silver halide grains at 40 ° C. for 20 minutes.

The above emulsion was coated in the same manner with a silver amount of ² g / m ² . The obtained coating samples were coated with coating samples C-1 ′ and D-
1 ', C-2', C-3 ', C-4', C-5 ', D-
2 ′, D-3 ′, D-4 ′ and D-5 ′.

The coated sample prepared as described above was subjected to 10 ^-3 with an Easy & G (EG & G) sensitometer.
After blue exposure for 2 seconds, development processing was performed. The developer is MA
A-1 developer was used at 20 ° C. for 10 minutes.

Table 2 shows the obtained results.

[0129]

Table 2 Emulsion Protecting Dopant Relative Blue Tone Intrinsic desensitization width (* 3) Colloid sensitivity (* 1) (* 2) ΔlogE reference ────────────────────────────── ────── C-1 gelatin-100 1.5-0.67 Comparative Example D-1 (7) -85 1.3-0.60 Comparative Example C-2 Gelatin [Fe (CN) ₆ ] ^{4 -} 30 1.8 -0.35 Comparative example C-3 gelatin ^{_{[Ru (CN) 6] 4-}} 45 1.9 -0.33 Comparative example C-4 gelatin ^{_{[Co (CN) 6] 3-}} 20 1. 9 -0.40 Comparative example C-5 gelatin ^{_{[Re (CN) 6] 4-}} 25 1.9 -0.38 Comparative example D-2 (7) [Fe (CN) 6] 4- 130 2.0 - 0.23 invention D-3 (7) [Ru (CN) 6] 4- 135 2.1 -0.22 present invention D-4 (7) [Co (CN) 6] 3- 125 2.1 - 0.25 Invention D-5 (7) [Re (CN) 6] 4- 140 2.0 -0.20 present invention ──────────────────────── ────────────

(* 1) Relative value of the reciprocal of the exposure amount that gives fog + density of 0.1 for samples C-1 to D-5 coated with spectral sensitizing dye blanks. (* 2) Spectral sensitizing dye blank samples C-1 to D
-5 represents the slope of the straight line portion of the characteristic curve. (* 3) Spectral sensitizing dye blank coated samples C-1 to D
-5 and coated samples C-1 'to D containing the spectral sensitizing dye.
The logarithmic difference of the exposure amount E giving a fog + density of -5 '.

As is apparent from Table 2, the emulsion in which gelatin and the dopant coexist has a significant adverse effect on the intrinsic sensitivity due to the interaction between gelatin and the transition metal complex.
A light-sensitive material using the emulsion of the present invention has high intrinsic sensitivity and high contrast at high illuminance, and remarkably improves intrinsic desensitization by a spectral sensitizing dye.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-20854 (JP, A) JP-A-4-110935 (JP, A) JP-A-2-166442 (JP, A) JP-A-58-1983 111937 (JP, A) JP-A-59-86040 (JP, A) JP-A-4-151140 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 1/09 G03C 1 / 015 G03C 1/04 G03C 1/047 G03C 1/07

Claims (3)

(57) [Claims] 1. A photographic material having a silver halide emulsion layer on a support, wherein the silver halide emulsion partially or entirely undergoes nucleation and / or crystal growth in the presence of a six- coordinate cyano complex. is performed, thereby saw including a hexacoordinated cyano complexes in the crystal lattice, further 10 g / Ag mole of Zerah
Synthetic polymer having protective colloid properties in the presence of tin
Perform steps from nucleation to chemical sensitization in the presence of compound
After completion of the chemical sensitization, gelatin was used as a binder for 30 minutes.
A silver halide photographic material, which is a silver halide emulsion obtained by adding 1 mol or more of g / silver . 2. A chemical sensitization from the nucleus shape formed gelatin absence
2. The silver halide photographic material according to claim 1, which has been subjected to the following steps . 3. The method according to claim 1, wherein fine silver halide grains prepared in the presence of a synthetic polymer compound having protective colloidal properties are supplied, so that a part of nucleation and / or crystal growth of said silver halide emulsion or 3. The silver halide photographic material according to claim 1, wherein all of the steps are performed.