JPH0643575A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material having a high sensitivity even at high illuminance, has a hard contrast and a high spectral sensitization sensitivity with the lesser intrinsic desensitization by spectral sensitizing dyestuff. CONSTITUTION:This photographic material has silver halide emulsion layers on a base and is constituted by incorporating novel silver halide particles into the emulsion layers. The above-mentioned silver halide emulsion is formed by subjecting the emulsion to a part or whole of the nucleus formation and/or crystal growth in the presence of <=10g/silver mol gelatin, more preferably in the absence of the gelatin and in the presence of a synthetic high-polymer compd. having a protective colloidal characteristic and hexacoordination cyanocomplex and includes the hexacoorclination cyanocomplex in the crystal lattice. The supply of silver and halogen in the nucleus formation and/or crystal growth of the silver halide particles to be incorporated into this silver halide emulsion is preferably executed by supplying the very small silver halide particles prepd. in the presence of the synthetic high-polymer compd. having the protective colloidal property.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic material. In particular, the present invention provides a high-sensitivity halogenation with improved spectral sensitivity, which is improved in high-intensity reciprocity law failure, has high contrast, high sensitivity in specific absorption, and has little 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) for incorporating a substance other than silver or a halide ion (this is referred to as a dopant) into a silver halide crystal has been well known.
In particular, many studies have been conducted on the technique for doping transition metals (Group 3-12 of the Periodic Table) for the purpose of modifying silver halide emulsions. For example, Tribery and Smith (Tr
ivelli and Smith) in U.S. Pat. No. 2,448,060, describes the formula R ₂ MX _{6 where} R is hydrogen, an alkali metal or ammonium group, M is a trivalent transition metal of palladium or platinum, and X is It is a halogen atom)
A transition metal compound represented by the following formula: -any step of producing silver halide-that is, before or during precipitation of silver halide, or before or during first ripening (physical ripening), or second ripening It is disclosed that the silver halide emulsion can be sensitized by adding it before (chemical ripening) or during-ripening.

There is a remarkable difference in the photographic effect of the transition metal compound in the silver halide emulsion between the case where the transition metal compound is added during the formation of the silver halide grains and the case where it is added after the precipitation of the 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 and effectively alters photographic performance despite its very small amount. When the transition metal is added after the formation of silver halide grains is completed, the transition metal is adsorbed on the surface of the grain, but the transition metal is often inaccessible to the grain due to the interaction with the protective colloid. After the particles are formed, a transition metal is added,
To obtain the same effect as when the transition metal is incorporated as a dopant inside the silver halide grain, it is necessary to add a higher concentration of the transition metal. That is, it is generally recognized that when a transition metal is added during chemical sensitization, it is difficult to obtain a photographic effect, and the transition metal has been added during the formation of silver halide grains and used as a dopant. Regarding the technical difference between a metal dope by adding a metal compound during the formation of silver halide grains and a metal sensitizer by adding the metal compound to an emulsion after the formation of silver halide grains, Research Disclosure ( Research Disclosure), Volume 176, December 1978.
Monthly publication, Item 17643, chapter IA describes transition metal compounds added during grain precipitation, and chapter IIIA describes transition metal compounds introduced during chemical sensitization.

In US Pat. No. 3,790,390,
Simple salts of metals of the 4th period of the periodic table of elements such as iron, cobalt and nickel, and hexacoordinated complexes containing cyano ligands, ruthenium, rhodium, palladium, osmium, iridium simple salts or halide ligands only The use of a hexacoordinated complex according to US Pat. This describes a silver halide emulsion containing a hexacoordinated cyano complex of iron (II), iron (III) and cobalt (III).

In US Pat. No. 4,126,472, 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 surface-doped or grain-formed. Use as a surface modifier is disclosed. However, here 6
There is no description of a coordination cyano complex.

European Patent No. 0242190 describes
A silver halide emulsion having silver halide grains formed in the presence of at least one complex compound of trivalent rhodium having 3, 4, 5 or 6 cyanide ligands has a high illumination failure. It has been disclosed to reduce.

US Pat. No. 3,690,888 discloses a process for the preparation of silver halides containing polyvalent metal ions, which comprises the step of making silver halides in the presence of protective colloids which consist mainly of acrylic polymers. ing.
It specifically mentions bismuth, iridium, lead and / or osmium ions as polyvalent metal ions, but there is no description of hexacoordinate cyano complexes.

In these disclosure examples, it is not clearly shown that the ligand is incorporated into the particles together with the transition metal, and the definition of the ligand of the transition metal complex compound and its effect are also described. Not not.

On the other hand, European Patent Nos. 0336425 and 03
Nos. 36426, JP-A-2-20853 and 2-
20854 discloses that in the presence of a hexacoordinated rhenium, ruthenium, osmium, and iridium metal complex having at least four cyan ligands, the sensitivity and gradation are excellent in stability over time, and low illumination failure is improved. Described silver halide emulsions are described. Also, European Patent 033
No. 6427 and JP-A-2-20852 disclose 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 law failure are disclosed. Moreover, European Patent No. 0336689 specification,
In JP-A-2-20855, the sensitivity is controlled by a metal complex in which a ligand of a hexacoordinated rhenium complex is a combination of halogen, nitrosyl, thionitrosyl, cyan, water, and thiocyan, and a low illuminance reciprocity law failure is reported. An improved emulsion is disclosed. Furthermore, JP-A-3-118535
The publication discloses a transition metal complex in which one ligand of a hexacoordinated metal complex is carbonyl, and the publication describes a transition metal complex in which two ligands of a hexacoordinated metal complex are oxygen. It is disclosed that the emulsion contained therein is effective for photographic performance.

In these disclosures, the hexacoordinated transition metal complex is composed of one silver ion inside the silver halide crystal structure and seven vacancies from which six halogen ions adjacent to the silver ion are removed. It has been recognized that it is housed in space, which is different from the conventional belief that transition metals are incorporated into silver halide grains as single ions or atoms.

However, in these disclosed examples, ordinary gelatin is used as the protective colloid when the silver halide grains doped with the metal complex are formed. For the interaction between metal and gelatin, see Theory of Photographic Process, 4th edition, Macmillan, Inc. (TH
James, "The Theory of the Photographic Process" 4th
ed. Macmillan), Chapter 2 (pp. 71-72). It has been shown that precious metals such as gold and platinum, iridium and other heavy metals interact with gelatin to form complex salts and reduce metals. Therefore, in the conventional transition metal complex compound doping technique, the unexpected effects such as the oxidation or reduction of the transition metal due to the interaction between the transition metal complex and gelatin, the exchange of the ligand of the transition metal complex, and the decomposition are sufficient. I couldn't control it.

[0012]

An object of the present invention is to control the transition metal complex by minimizing the interaction between gelatin and the transition metal complex when the silver halide emulsion is doped with the transition metal complex. The purpose of this is to maximize the effect obtained by doping the transition metal complex.

[0013]

The objects of the present invention are: (1) a photographic material having a silver halide emulsion layer on a support, wherein the silver halide emulsion comprises 10 g / silver of 1 mol or less of gelatin. In the presence of a synthetic polymer compound having a protective colloidal property and a hexacoordinated cyano complex, part or all of nucleation and / or crystal growth is performed, whereby the hexacoordinated cyano complex is formed into a crystal lattice. A silver halide photographic material characterized by being a silver halide emulsion contained therein; (2) A part or all of nucleation and / or crystal growth was carried out in the absence of gelatin. (3) silver halide photographic material; and (3) by supplying fine silver halide grains prepared in the presence of a synthetic polymer compound having a protective colloidal property, nucleation and / or Other was achieved by a silver halide photographic material according to some or all of the crystal growth is performed (1) or (2).

With the above photographic materials, unexpected adverse effects on photographic performance due to oxidation or reduction of transition metals, exchange of ligands, decomposition, etc. caused by interaction of hexacoordinate cyano complex salts with gelatin are minimized. The effect on the photographic performance of the silver halide doping of the hexacoordinated cyano complex ion could be maximized with the limit.

The present invention will be described in more detail below. The hexacoordinated cyano complex salt used in the present invention is a salt containing a hexacoordinated transition metal complex ion satisfying the following (I). Formula (I) [M (CN) ₆ ] ^{n-In the} formula, M is Group 5, Group 6, Group 7, or Group 8 of the 4th, 5th, and 6th periods of the periodic table of the elements. A transition metal selected from Group 10, Group 9 and Group 10, preferably iron, cobalt, ruthenium, rhenium, rhodium,
Osmium and iridium; n is 3 or 4.

The counter cation has little importance because the hexacoordinated metal complex salt dissociates when introduced into an aqueous medium such as that used to form silver halide grains. 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 for hexacoordinated transition metal complex salts which meet the requirements of the invention.

The above hexacoordinate cyano complex ion is incorporated into the silver halide grain crystal. In other words, a hexacoordinated cyano complex ion is a space formed by removing 7 silver vacancies from one silver ion inside the crystal structure and 6 halogen ions adjacent to it (7 vacancies) Housed in. Since these 7 vacancies show a net charge of -5, anion complexes such as hexacoordinated cyano complex ions are easily incorporated into the crystal lattice, and hexacoordinated transition metal complexes are also included. The ability to trap photoholes or electrons in γ is expected to depend on the magnitude of the difference between the charge of the introduced complex and the charge of the 7 vacancies.

In the hexacoordinated cyano complex salt, the central transition metal ion can occupy the position of the silver ion, and the six cyano ions can occupy the positions of the six halogen ions adjacent to the substituted silver ion. And is spatially similar to the 7 vacancies. Also in terms of atomic size, silver ion is much smaller than bromide ion, silver bromide crystal can accommodate iodine ion larger than bromide ion, and further, cyano ligand of transition metal complex. A hexacoordinated cyano complex salt has seven vacant spaces inside a silver halide crystal because the bond distance between the core and the central transition metal is reduced and the size of the transition metal complex is reduced. It can be understood that it is substituted with the child point ion and is taken into the inside of the silver halide crystal.

The hexacoordinated cyano complex salt satisfying the requirements of the present invention can be incorporated in silver halide grains at the same concentration per mol of silver as has been conventionally used in transition metal doping. . In this regard, an extremely wide range of densities are known, and it is known from JP-A-51-10712.
From the low concentration of 10 ^-10 mol per mol of silver disclosed in US Pat. No. 9,873,676 and US Pat.
No. 0891 10 disclosed per mol of silver disclosed in each specification
^{-Used in} the high concentration range of ^-3 molar. The effective concentration varies 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 hexacoordinated cyano complex salt is 10 ^-8 to 10 ^-3 mol per mol of silver. Is more preferable.

Regarding the doping amount and the doping ratio of the hexacoordinate cyano complex salt in the silver halide grains, the central transition metal of the doped 6 cyano complex salt is analyzed by atomic absorption spectrometry, ICP method (Indu
ctively Coupled Plasma Spectrometry: ICPMS method (Inductivel)
y Coupled Plasma Mass Spectrometry: etc.) and the like.

The hexacoordinate cyano complex salt used in the present invention is
It can be optionally added during the preparation of the silver halide grains, that is, during part or all of the nucleation and / or the crystal growth. As a more preferred embodiment, it is more preferable that the doping amount is large in the vicinity of the grain surface of the silver halide grain, but it is also preferable that the concentration is high in a region slightly deeper than the grain surface of the silver halide grain. 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 hexacoordinate cyano complex salt used in the present invention is preferably added after being dissolved in water or a suitable solvent. In order to stabilize the solution, a method of adding an alkali metal halide aqueous solution (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. Moreover, you may add alkali etc. as needed.

The hexacoordinated cyano complex salt used in the present invention is added directly to the reaction solution at the time of silver halide grain formation, or
It is preferably contained by adding it to an aqueous solution of a halide for forming silver halide grains or to a solution other than that to form grains. Furthermore, various addition methods can be combined.

Further, nucleation of silver halide grains and / or
Alternatively, when part or all of the crystal growth is carried out by supplying a silver halide emulsion containing fine silver halide grains prepared in the presence of a synthetic polymer compound having a protective colloid property, 6 The cyano complex salt may be supplied by doping in fine silver halide grains, or may be supplied alone in the reaction vessel.

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

The hexacoordinate cyano complex salt used in the present invention can be used alone or in combination of two or more kinds. It can also be used in combination with other metal ions. Other metal ions are added in the form of a salt that can be dissolved at the time of grain formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydroxide salt or hexacoordinated complex salt, and tetracoordinated complex salt. it can.

The following are used as the polymer compound having a protective colloid action on the silver halide grains used in the present invention.

A. Polyacrylamide Polymer A homopolymer of acrylamide, US Pat. No. 254147.
No. 4, a copolymer of polyacrylamide and imidized polyacrylamide, West German Patent 120
No. 2132, a copolymer of acrylamide and methacrylamide, a partially aminated acrylamide polymer shown in US Pat. No. 3,284,207, JP-B-45-14031, US-371.
No. 3834, No. 3746548, British Patent 78834
No. 3 Substituted acrylamide polymer shown in each specification.

B. Amino Polymer US Pat. Nos. 3,345,346, 3,706,504 and 4,
No. 350759, West German Patent No. 2138872, amino polymers shown in each specification, British Patent No. 1413125
U.S. Pat. No. 3,425,836, polymers having quaternary amines, U.S. Pat. No. 3,511,818, polymers having amino and carboxyl groups, U.S. Pat. No. 3,832,185.

C. Polymer Having Thioether Group 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 Pat. No. 3,0007.
41, an organic acid monoester of polyvinyl alcohol, a maleic acid ester shown in US Pat. No. 3,236,653, and a copolymer of polyvinyl alcohol and polyvinylpyrrolidone shown in US Pat. No. 3,479,189.

E. Acrylic acid polymer Acrylic acid homopolymer, US Pat. No. 3,832,185,
No. 3852073, Acrylic ester polymers having amino groups shown in US Pat. No. 4,131,147.
Halogenated acrylic acid ester polymers shown in No. 1 and cyanoalkyl acrylic acid esters shown in US Pat. No. 4,120,727.

F. Polymers having hydroxyquinoline Polymers having hydroxyquinoline shown in U.S. Pat. Nos. 4,030,929 and 4,152,161. G. Cellulose and starch derivatives British Patents 542704, 551659, US 2127573, 2311086, and 23220
No. 85 Cellulose or starch derivative shown in each specification.

H. Acetal US Pat. Nos. 2,358,836, 3,0038,79 and 2,
The polyvinyl acetal shown in each specification of 828204, British Patent 771155.

I. Polyvinylpyrrolidone Homopolymer of vinylpyrrolidone, French patent 203
A copolymer of acrolein and pyrrolidone shown in 1396.

J. Polystyrene Polystyrylamine polymers shown in U.S. Pat. No. 4,315,071, halogenated styrene polymers shown in U.S. Pat. No. 3,861,918.

K. Imidazole polymer JP-B-43-7561, 47-25374, 5
No. 2-16365, German Patent 2012095
Nos. 1,202,970, and polymers having vinylimidazole groups shown in the respective specifications.

L. Others A vinyl polymer having an azaindene group described in JP-A-59-8604, a polyalkylene oxide derivative described in U.S. Pat. No. 2,976,150, a polyvinylamine imide polymer described in U.S. Pat. No. 4,022,623, U.S. Pat. No. 4,294,920. Issue 408
9688 Polymers shown in US Pat.
No. 84456, polyvinyl pyridine, US Pat. No. 3,520,857, imidazole group-containing vinyl polymer, JP-B No. 60-658, and triazole group-containing vinyl polymer, The Photographic Society of Japan, Vol. 29. 1, polyvinyl-2-methylimidazole and acrylamide-imidazole copolymers shown on page 18, and water-soluble polyalkyleneaminotriazoles shown on ZEITSCHLIFT BISENSCHRIICH PHOTOGRAPHY, Vol. 45, page 43 (1950). Can be mentioned.

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

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 a protective colloid property, and the content of gelatin at that time is It is preferably at most 10 g / silver mole and more preferably free of gelatin.

Further, nucleation of silver halide grains and / or
Alternatively, after crystal growth, gelatin may be additionally added in the steps of washing with water / desalting to chemical sensitization. The gelatin content is preferably 200 g / silver mole or less, and 10
It is more preferably 0 g / silver mole or less, and 10 g /
It is more preferably not more than silver mole, and most preferably not containing gelatin at all. However, in the stage from the end of chemical sensitization to immediately 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. RESEAECH DIS for available vehicles
CLOSURE Volume 176 Item 17643 can be referred to. In the present invention, the temperature during grain formation is 10
C. to 95.degree. C., preferably 40.degree. C. to 80.degree.

In the present invention, fine silver halide grains prepared in the presence of a synthetic high molecular compound having a protective colloid property for part or all of nucleation and / or crystal growth of silver halide grains are used. It is preferably carried out by supplying the contained silver halide emulsion.
Regarding this technique, JP-A-1-183417 and JP-A-1-183417
-183644, 1-183645, 2-43
No. 534, No. 2-43535 and No. 2-44335.
Publications, US Pat. No. 4,879,208 and European Patent 0
The technique is disclosed in each specification of No. 408752.

The concentration of the synthetic polymer compound having a protective colloid property used is not particularly limited, but for emulsions containing fine silver halide grains, it is preferably 20% by weight or less, and 10% by weight. % Or less, and more preferably 5% by weight or less.

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

Further, gelatin may be additionally added in the steps of washing with water / desalting to chemical sensitization. The content of this gelatin is preferably not more than 200 g / silver mole, and 100
It is more preferably at most g / silver mole, and further 10
It is more preferably g / silver mole or less, and it is more preferable that gelatin is not contained at all. However, in the stage from the end of chemical sensitization to immediately 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. RESEAECH D for available vehicles
The description of ISCLOSURE Volume 176 Item 17643 can be referred to. In the present invention, the temperature during grain formation is 1
It is in the range of 0 ° C to 95 ° C, preferably 40 ° C to 80 ° C.
Is the range. The temperature at the time of forming fine silver halide grains 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 directly using a transmission electron microscope. The magnification at this time is preferably 20,000 times to 40,000 times. 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 silver halide composition of the emulsion obtained by the present invention is silver bromide, silver chloride, silver iodobromide, silver iodochloride,
It may be either silver chlorobromide or silver iodochlorobromide. The grain size of the silver halide grains of the present invention is not particularly limited, but is 0.05 μm to 10 μm, preferably 0.1 μm to 3 μm. The size of the silver halide grain of the present invention can be adjusted by controlling the temperature and pAg, selecting the kind and amount of solvent, the silver salt used during grain growth, and the addition rate of halide.

As the silver halide solvent often used, thiocyanates, thioethers, thioureas and the like can be mentioned, and ammonia can also be used in combination so long as it does not have an adverse effect. For example, thiocyanate (US Pat. Nos. 2,222,264 and 24,485).
34, 3320069, etc.), thioether compounds (for example, US Pat. Nos. 3,271,157, 35).
No. 74628, No. 3704130, No. 4297439
Nos. 4,276,347 and the like) and thione compounds (for example, JP-A Nos. 53-144319 and 53-824).
No. 08, No. 55-77737, etc.), amine compounds (for example, JP-A No. 54-100717, etc.) and the like can be used.

The silver halide grains according to the present invention have a regular crystal form (normal grain) such as a hexahedron, an octahedron, a dodecahedron, a tetrahedron, an icosahedron and an octahedron. It may have a spherical or potato-like irregular crystal shape, and particles of various shapes having one or more twin planes, especially two or three parallel twin planes. It may be a hexagonal tabular grain and a triangular tabular twin crystal grain.

For the production of the silver halide emulsion used in the present invention, any method known so far can be used. That is, the silver salt aqueous solution and the halogen salt aqueous solution are added to a reaction vessel containing the gelatin aqueous solution under efficient stirring. As a concrete method, P. Glafkides
By Chemie et Phisique Photographique (Paul Montel
(Published 1967), by GF Duffin Photographic Emulsi
on Chemistry (Published by The Focal Press, 1966), VL
Making and Coating Photographic by Zelikman et al
It can be prepared by the method described in Emulsion (The Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Good. As one form of simultaneous mixing method,
It is also possible to use a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method. Also, British Patent 1535
No. 016, Japanese Patent Publication No. 48-36890, No. 52-
No. 16364, US Pat. No. 4,242,445, JP-A No. 55-158124, etc., a method of changing the addition rate of silver nitrate or an alkali halide aqueous solution according to the grain growth rate, as described in JP-A-16364, etc. It is preferable to grow rapidly in a range not exceeding the critical supersaturation degree by using a method of changing the concentration of the aqueous solution as described in 1. These methods are preferably used because re-nucleation does not occur and 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 part) and the outside (shell part) of 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 wrapping structure described above but also a so-called junction structure can be prepared. Examples of these are disclosed in JP-A-59-133540 and JP-A-58-58.
No. 108526, European Patent No. 199,290A2
Specification, Japanese Patent Publication No. 58-24772, Japanese Patent Laid-Open No. 59-1
No. 6254, for example.

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 has a uniform halogen composition or has a core-shell type structure.

In the case of a junction structure, it is naturally possible to combine silver halides, but a silver salt compound not having a rock salt structure such as silver rhodan and silver carbonate may be combined with silver halide to form a junction structure. In addition, a non-silver salt compound such as PbO may also be used as long as a junction structure is possible.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the silver iodide content of the core part is high and the silver iodide content of the shell part is low, Conversely, grains having a low silver iodide content in the core part and a high silver iodide content in the shell part may be used. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and the silver iodide content in the junction crystal being relatively low, or vice versa. Also,
The boundary portion of the grains having these structures, which have different halogen compositions, may be a clear boundary or an unclear boundary by forming a mixed crystal due to a difference in composition, and it is positively continuous. It may have a structural change.

The silver halide emulsion used in the present invention is EP
-0096727B1, EP-0064412B1 and the like, or treatments for rounding particles, or surface modification as disclosed in DE-2306447C2 and JP-A-60-221320. You may do quality.

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 emulsion can be prepared by selecting a developing solution or developing conditions. The emulsion of can also be used.
A shallow internal latent image type emulsion covered with a thin shell can also be used according to the purpose.

In the present invention, it is preferable to use silver halide grains having dislocation lines. A grain having dislocation lines is disclosed in US Pat. No. 4,806,461.

The emulsion of the present invention is usually spectrally sensitized. Examples of dyes used for this purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Examples include styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. As the basic heterocyclic nucleus, any of the nuclei normally used for cyanine dyes can be applied to these dyes. 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, etc .; Condensed nuclei: and nuclei in which aromatic hydrocarbon rings are condensed to these nuclei, that is, indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzimidazole nuclei, naphthimidazole nuclei, A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzoterrazole nucleus and the like can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

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

These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US 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,
3614609, 3838762, 4026
No. 707, British Patent Nos. 1344281 and 150780.
No. 3, each specification, Japanese Patent Publication Nos. 43-4936 and 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925, etc.

Furthermore, these sensitizing dyes are dyes that do not exhibit a spectral sensitizing effect by themselves, or substances that do not substantially absorb visible light and are combined with sensitizing dyes to achieve remarkable spectral sensitization. It may be used in combination with any compound known to be called a so-called supersensitizer which exhibits an increase. Typical examples of the supersensitizer include bispyridinium salt compounds described in JP-A-59-142541, stilbene derivatives described in JP-B-59-18691, 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 US Pat. No. 3,743,510, cadmium salts, azaindene compounds and the like. Can be mentioned. The sensitizing dye is added after chemical ripening or before chemical ripening. For the silver halide grains of the present invention, it is most preferred that the sensitizing dye is added during chemical ripening or before chemical ripening (for example, during grain formation and 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 sulfur sensitization, unstable sulfur compounds were used, and P. Grafkides, Chimie et Physique Photograph.
ique (Paul Momtel, 1987, 5th edition), Research
Unstable sulfur compounds described in Disclosure magazine 307, volume 307105 and the like can be used. Specifically, thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-
Ethyl-N '-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (for example, thioacetamide), rhodanines (for example, diethylrhodanine, 5-benzylidene-N-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, cystine), polythionates, elemental sulfur, and active gelatin can also be used.

In the selenium sensitization, an unstable selenium compound is used, and Japanese Patent Publication Nos. 43-13489 and 44-157.
48, JP-A-4-25832 and 4-109240.
Publications, Japanese Patent Application Nos. 3-53693 and 3-82929
Unstable selenium compounds described in each specification can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenamides (eg, selenoacetamide, N, N-diethylphenyl selenamide), phosphine selenides (for example, triphenylphosphine selenide, pentafluorophenyltriphenylphosphine selenide), selenophosphates (for example, tri-p-tolyl selenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids,
Selenoesters and diacyl selenides may be used. Furthermore, Japanese Patent Publications Nos. 46-4553 and 52-3.
Non-unstable selenium compounds described in Japanese Patent No. 4492, etc.,
For example, selenious acid, potassium selenocyanide, selenazoles, selenides and the like can be used.

In tellurium sensitization, an unstable tellurium compound is used, and Canadian Patent No. 800958 and British Patent 129 are used.
Nos. 5462, 1396696, Japanese Patent Application No. 2-
No. 333819, No. 3-53693, No. 3-1315
Unstable tellurium compounds described in the respective specifications of No. 98 and No. 4-129787 can be used. Specifically, telluroureas (for example, tetramethyl tellurourea, N, N'-dimethylethylene tellurourea, N, N '
-Diphenylethylene tellurourea), phosphine tellurides (eg, butyl-diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) telluride (Eg, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), isosterocyanates, Telluroamides, tellurohydrazides, telluroesters (eg butylhexyl telluroester), 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.

Regarding the sensitization of precious metals, the above-mentioned P. Grafkid
es, Chimie et Physique Photographique (Paul Momt
el company, 1987, 5th edition), Research Disclosure magazine 3
07, 307105, etc., gold, platinum,
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, US Pat. Nos. 2,642,361, 5,049,484 and 50,494 are added.
The gold compounds described in each specification of No. 85 can also be used.

Regarding reduction sensitization, the above-mentioned P. Grafkides
By Chimie et Physique Photographique (Paul Momtel
(Published in 1987, 5th edition), Research Disclosure magazine 30
Known reducing compounds described in Volume 7, No. 307105 and the like can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (eg, dimethylaminoborane), hydrazine compound (eg, hydrazine, p-tolylhydrazine), polyamine compound (eg, diethylenetriamine, triethylene). Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas and the like may be used. Further, reduction sensitization may be carried out in an atmosphere of high pH or silver ion excess (so-called silver ripening).

These chemical sensitizations may be used alone or in combination of two or more kinds. When they are 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 used, the chemical sensitization conditions and the like, but it is 10 ^-8 to 10 per mol of silver halide.
^-2 mol, preferably about 10 ^{-7 to} 5 × 10 ^-3 mol is used.

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

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, azoles, for example, benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds), heterocyclic mercapto compounds, for example, mercaptothiazoles, mercapto Benzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (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 oxazoline thione; Azaindenes such as tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); Benzes Thiosulfonic acids; benzenesulfinic acid; can be added to many compounds known as antifoggants or stabilizers, such as.

The antifoggant or stabilizer is usually added after chemical sensitization, but more preferably during chemical ripening or before the start of chemical ripening. .

The emulsion of the present invention has one emulsion layer or two.
It can be used for a photographic light-sensitive material having an arbitrary layer structure, regardless of whether it has more layers. A silver halide multilayer color photographic light-sensitive material using the emulsion of the present invention has a multiple structure in which emulsion layers containing a binder and silver halide grains are superposed for separately recording blue light, green light and red light. However, each emulsion layer is composed of at least two layers, a high sensitivity layer and a low sensitivity layer.

The silver halide emulsion of the present invention can be applied to a color light-sensitive material as described above, but any other light-sensitive material may be used regardless of whether the emulsion layer is a single layer or a multilayer, for example, an X-ray light-sensitive material, black and white. It can be similarly applied to a photosensitive material for photographing, a photosensitive material for plate making, a printing paper and the like.

Various additives for the silver halide emulsion of the present invention, for example, binders, chemical sensitizers, spectral sensitizers, stabilizers, gelatin hardening agents, surfactants, antistatic agents, polymer latices, matting agents. , A color coupler, an ultraviolet absorber, an anti-fading agent, a dye and a support of a light-sensitive material using these emulsions, a coating method, an exposure method, a development processing method and the like are not particularly limited, and examples thereof include Research Disclosure 176, Item 17643 (RD-17
643), the same volume 187, item 18716 (RD-1
8716) and 225, item 22534 (R
The description of D-22534) can be referred to.

Descriptions of these Research Disclosures are shown in the following list. ──────────────────────────────────── Additive type RD17643 RD18716 RD22534 ───────── ──────────────────────────── 1 Chemical sensitizer page 23 648 right column page 24 2 Sensitivity enhancer Same as above 3 Spectral sensitization Agents 23 to 24 pages 648 right column to 24 to 28 supersensitizers 649 right columns 4 whitening agents 24 pages 5 antifoggants 24 to 25 pages 649 right columns to 24 pages, 31 and stabilizers 6 light absorber, page 25-26 page 649 right column-filter dye page 650 left column ultraviolet absorber 7 stain inhibitor page 25 right column page 650 left-right column 8 dye image stabilizer 25 page 32 page 9 hardening Agents Page 26 651 Left column Page 28 10 Binders Page 26 Same as above 11 Plasticizers and lubricants Page 27 65 Page right column 12 Coating aid, surface 26 to 27 pages Same as above Activator 13 Antistatic agent Page 27 same as above 14 Color coupler 25 pages 649 pages 31 pages ─────────────────── ──────────────────

The color coupler used in the present invention preferably has a ballast group or is polymerized to be diffusion resistant. 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, because the coated silver amount can be reduced. Further, a coupler in which the coloring dye has an appropriate diffusibility, a non-coloring coupler or a DIR coupler which releases a development inhibitor upon coupling reaction,
Alternatively, couplers that release development accelerators can also be used.

A typical example of the yellow coupler which can be used in the present invention is an oil protect type acylacetamide type coupler. A typical example thereof is an oxygen atom releasing yellow coupler or a nitrogen atom releasing yellow coupler. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an amylamino group, from the viewpoint of the hue and color density of the color forming dye.

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

The cyan couplers usable in the present invention include oil-protection type naphthol type and phenol type couplers, and the naphthol type couplers described in US Pat. No. 2,474,293, preferably US Pat. Nos. 4,052,212 and 4,146,396. , Ibid.
Representative examples thereof include oxygen atom-elimination type two-equivalent naphthol couplers described in JP-A Nos. 33 and 4296200.

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

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Examples of such couplers include specific examples of magenta couplers in US Pat. No. 4,366,237 and British Patent 2,125,570, and EP 96570 and West German Patent Publication 32.
In each specification of No. 34533, specific examples of yellow, magenta or cyan couplers are described.

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

In the light-sensitive material of the present invention, a compound capable of releasing a nucleating agent or a development accelerator or a precursor thereof (hereinafter referred to as "development accelerator") in an image during development can be used. Typical examples of such compounds are described in British Patent Nos. 2097140 and 2131188, and a coupler which releases a development accelerator and the like by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. , 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, di-
2-Ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tridecyl phosphate) Butoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexylpheninephosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, 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, etc., aniline derivatives (N,
N-dibutyl-2-butoxy-5-tert-octylaniline and the like), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene and the like) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher,
Preferably, an organic solvent having a temperature of 50 ° C. or more and about 160 ° C. or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

Examples of gelatin hardening agents include active halogen compounds (2,4-dichloro-6-hydroxy-).
1,3,5-triazine and its sodium salt)
In addition, active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane or vinyl-based polymers having a vinylsulfonyl group in the side chain) are hydrophilic colloids such as gelatin. It is preferable because it cures quickly and gives stable photographic characteristics. N-carbamoylpyridinium salts (1
-Morpholinocarbonyl-3-pyridinio) methanesulfonate and the like) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate and the like) are also fast and excellent in curing rate.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is generally subjected to washing treatment or stabilizing treatment after development, bleach-fixing or fixing treatment. In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. A typical example of the stabilizing treatment is a multi-stage countercurrent stabilizing treatment as described in JP-A-57-8543 instead of the water washing step.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, 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-
Mention may be made of N-ethyl-N-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Two or more of these compounds can be used in combination depending on the purpose.

When carrying out the inversion process, normally,
Black and white development is performed, and then color development is performed. This black-and-white developer contains dihydroxybenzenes such as hydroquinone, 1
Known black-and-white developing agents such as 3-pyrazolidones such as -phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

P of these color developers and black and white developers
H is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and 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 bleached. The bleaching process may be performed at the same time as 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 processing after bleaching processing may be used. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in bleaching and bleach-fixing solutions. The pH of a bleaching solution or a bleach-fixing solution containing these aminopolycarboxylic acid iron (III) complex salts is usually 5.5.
~ 8 but lower pH for faster processing
It can also be processed with.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
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 particularly US Pat. No. 3,893,858 and West German Patent 129.
Compounds described in each specification of No. 0812 and JP-A No. 53-95630 are preferable. Further, US Pat.
The compounds described in No. 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 is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent and forward flow, and various other conditions Can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Pictur.
e and Television Engineers Volume 64, p. 248-
253 (May 1955 issue).

[0095]

The present invention will be described in detail below with reference to 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 and dissolved in 866 cc of water, and 0.083 M (mol / l) aqueous silver nitrate solution (Solution 1 was added to the solution kept at 75 ° C. with stirring. ) 36 cc and 0.088 M potassium bromide aqueous solution (solution 2) 36 cc were added in 10 minutes, and subsequently, 176 cc of solution 1 and solution 2 were added in 7 minutes by a normal double jet method. After additionally adding 1.4 g of potassium bromide, a 0.82 M silver nitrate aqueous solution (solution 3) 1010c
c from the initial flow rate of 1.8 cc / min by accelerating the flow rate to 7
It was added over 8 minutes, and at the same time, 0.90 M potassium bromide aqueous solution (solution 4) was added to a silver potential of 0 mV (vs. saturated calomel electrode).
It was added by controlling so as to keep. Furthermore, 0.
51M silver nitrate aqueous solution (solution 5) was added to 578 cc and 0.5
24 1M aqueous solution of potassium bromide (Solution 6) 578cc
It was added at a constant flow rate in minutes. After the addition was completed, the temperature was lowered to 35 ° C., the soluble salts were removed by the usual sedimentation method, and then the temperature was brought to 40 ° C. again and the gelatin was additionally added to dissolve the solution.
Adjusted to 6.3. The obtained particles have a projected area diameter of 0.8μ.
m monodisperse silver bromide octahedron grains (variation coefficient: 10%).

"Emulsion B-1: Silver bromide octahedral emulsion using synthetic compound having protective colloid property" (comparative example) A synthetic protective colloid represented by the following (1) instead of gelatin in Emulsion A-1. Was formed in the same manner as Emulsion A-1 except that 2 g was used.

[0098]

[Chemical 1]

However, the sedimentation was carried out by natural sedimentation, washing with water three times by the decantation method to remove the soluble salts, and adjusting the pH.
Adjusted to 6.3. The obtained particles have a projected area diameter of 0.8μ.
m monodisperse silver bromide octahedron grains (variation coefficient: 10%).

[Emulsions A-2 to A-5: octabromide emulsion of silver bromide doped with hexacoordinated cyano complex salt using gelatin]
(Comparative Example) Solution 6 of Emulsion A-1 was added to the following (2), (3),
Except that (4) and (5) were dissolved in 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 ]

"Emulsions B-2 to B-5: a silver bromide octahedral emulsion doped with a hexacoordinated cyano complex salt using a synthetic compound having a protective colloid property" (invention) Solution 6 of emulsion B-1 And (2), (3),
Except that (4) and (5) were dissolved in 5 × 10 ⁻⁴ M,
Emulsions obtained in exactly the same manner as Emulsion B-1, B-2 and 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 emulsions with 1.2 × 10 ⁻⁵ mol / mol silver sodium thiosulfate and 3.6 × 10 ^−6. Optimum chemical sensitization was performed with mol / mol silver potassium chloroaurate and 5.1 × 10 ⁻⁴ mol / mol silver potassium thiocyanate. 2g of these
The amount of silver applied was / m ² . However, B-1, B-2, B
-3, B-4 and B-5 emulsions were
Gelatin was added as a coating binder.

The obtained coating samples were applied as 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, the spectral sensitizing dye shown in (6) below was added at 2.5 × 10 ⁻⁴ mol / mol silver immediately before coating, and halogen was added at 40 ° C. for 20 minutes. Adsorbed on silver halide grains.

[0108]

[Chemical 2]

The above emulsion was coated in the same manner with a silver amount of ² g / m ² . The obtained coated samples are coated 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 the following MA
It was carried out at 20 ° C. for 10 minutes using the A-1 developer.

──────────────────────────────────── MAA-1 Developer ─────── ─────────────────────────────── Metol 2.5g L-Ascorbic acid 10.0g Nabox 35g KBr 1.0g H ₂ O 1 liter ─────────────────────────────────────

The results obtained are shown in Table 1.

[0113]

[Table 1] Table 1 ──────────────────────────────────── Emulsion protection dopant Relative blue gradation 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 Invention B-5 (1) [Ir (CN) 6] 3- 125 2.0 -0.17 present invention ──────────────────────── ─────────────

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

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

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 were introduced into a mixer installed outside the reaction vessel, and 1% by weight gelatin aqueous solution as solution 7 was added to the above mixer as a third solution. Was prepared in the same manner as Emulsion A-1, except that the fine silver halide emulsion obtained by the simultaneous introduction as the above was fed into the reactor.

"Emulsion D-1: Silver bromide octahedron emulsion using synthetic compound having protective colloid property" (Comparative Example) Synthetic protective colloid represented by the following (7) in place of gelatin in Emulsion C-1. 2 g in a reaction vessel, or solution 2,
Emulsion C-1 was prepared in the same manner as in Solution 4, Solution 6 and Solution 7 except that 0.1% by weight was used.

[0118]

[Chemical 3]

However, the sedimentation was carried out by natural sedimentation, washing with water three times by the decantation method to remove soluble salts, and adjusting the pH.
Adjusted to 6.3.

"Emulsions C-2 to C-5: octabromide emulsion of silver bromide doped with hexacoordinated cyano complex salt using gelatin"
(Comparative Example) Solution 6 of Emulsion C-1 was added to (2), (4),
Except that (8) and (9) were dissolved in 5 × 10 ⁻⁴ M
Emulsions obtained in exactly the same manner as Emulsion C-1, C-2 and C
-3, C-4 and C-5 were prepared.

(8) K ₃ [Co (CN) ₆ ]

(9) K ₄ [Re (CN) ₆ ]

"Emulsions D-2 to D-5: Silver bromide octahedral emulsion doped with a hexacoordinated cyano complex salt using a synthetic compound having a protective colloid property" (invention) Solution 6 of emulsion D-1 And (2), (4),
Except that (8) and (9) were dissolved in 5 × 10 ⁻⁴ M
Emulsions obtained in exactly the same manner as Emulsion D-1, D-2 and 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 emulsions with 1.2 × 10 ⁻⁵ mol / mol silver sodium thiosulfate and 3.6 × 10 ^−6. Optimum chemical sensitization was performed with mol / mol silver potassium chloroaurate and 5.1 × 10 ⁻⁴ mol / mol silver potassium thiocyanate. 2g of these
The amount of silver applied was / m ² . However, D-1, D-2, D
-3, D-4 and D-5 emulsions were
Gelatin was added as a coating binder.

The obtained coating samples were coated 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 subjecting the emulsion to the chemical sensitization, 2.5 × 10 ⁻⁴ mol / mol silver is added to the spectral sensitizing dye shown in (6) 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 coated samples were coated samples C-1 ′, 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 the above-mentioned MA
It was carried out at 20 ° C. for 10 minutes using the A-1 developer.

The results obtained are shown in Table 2.

[0129]

[Table 2] Table 2 ──────────────────────────────────── Emulsion protection dopant Relative blue gradation 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 giving the fog + density of 0.1 of the coating samples C-1 to D-5 of the spectral sensitizing dye blank. (* 2) Spectral sensitizing dye blank coating samples C-1 to D
The slope of the straight line portion of the characteristic curve of -5 is shown, and the larger the value, the harder the image becomes. (* 3) Spectral sensitizing dye blank coating samples C-1 to D
-5 and coating samples C-1 'to D containing a spectral sensitizing dye
-5 ', the logarithmic difference of the exposure amount E giving a fog + density of 0.1.

It is clear from Table 2 that the emulsion in which gelatin and the dopant coexist has a remarkable adverse effect on the intrinsic sensitivity due to the interaction between the gelatin and the transition metal complex salt.
The light-sensitive material using the emulsion of the present invention has high intrinsic sensitivity and high contrast at high illuminance, and the intrinsic desensitization by the spectral sensitizing dye is remarkably improved.

Claims (3)

[Claims] 1. A photographic material having a silver halide emulsion layer on a support, wherein the silver halide emulsion is a synthetic polymer having a protective colloid property in the presence of 10 g / silver of 1 mol or less of gelatin. A part or all of nucleation and / or crystal growth is performed in the presence of the compound and the hexacoordinated cyano complex, whereby the silver halide emulsion is characterized by containing the hexacoordinated cyano complex in the crystal lattice. Silver halide photographic material to be used. 2. The silver halide photographic material according to claim 1, wherein a part or all of nucleation and / or crystal growth is carried out in the absence of gelatin. 3. By supplying minute silver halide grains prepared in the presence of a synthetic polymer compound having a protective colloidal property, a part of nucleation and / or crystal growth of the silver halide emulsion or A silver halide photographic material according to claim 1 or 2 which has been all done.