JPH0643574A - 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 chemical sensitization 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. 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) in which a substance other than silver or halide ions (this is referred to as a dopant) is contained in or in the surface of a silver halide crystal has been well known. Here, also on the surface of the silver halide grain, the dopant is embedded at the lattice position on the crystal surface in place of the ion that occupied it, or the lattice position where the silver or halogen ion above the grain surface should occupy It is considered that they are occupied by chemical adsorption on the particle surface, and can be considered as a dope in a broad sense. The surface doping can be distinguished from the doping in the bulk crystal lattice.

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, U.S. Pat. No. 244806 by Trivelli and Smith.
No. 0 is represented by the formula R ₂ MX ₆ (wherein R is hydrogen, an alkali metal or an ammonium group, M is a trivalent transition metal such as palladium or platinum, and X is a halogen atom). A transition metal compound at any stage of producing silver halide (ie, 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 before the chemical ripening or during the ripening).

There is a marked 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 silver halide grain formation is complete, the transition metal is surface-doped into the grain, but often cannot interact with the protective colloid to gain access to the grain. To obtain the same effect as when the transition metal is added after grain formation and incorporated into the silver halide grain as a dopant, it is necessary to add a higher concentration of 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 dope by adding a metal compound during the formation of silver halide grains and surface dope by adding a metal compound to the emulsion after the formation of silver halide grains, Research Disclosure , Volume 176 1978
Issue 17643, Chapter IA, Chapter IA, on transition metal compounds added during particle precipitation, and II
Section IA describes transition metal compounds introduced during chemical sensitization.

Although doping is certainly more efficient for incorporating transition metals into silver halide grains,
When the transition metal is incorporated inside the particles, the electrons generated by exposure are trapped inside the particles to form an internal latent image. This is a great inefficiency for the concentration of latent images to obtain high sensitivity. In other words, localizing the metal on the surface of the grain is very important for increasing the sensitivity of the silver halide emulsion. This is because, in the surface latent image type emulsion, since a latent image is formed on the surface of silver halide grains, it is considered advantageous that the transition metal that captures electrons is present on the surface.

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), but there is no description limited to grain surface doping.

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 iridium-containing. 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. Although it is disclosed that there is a decrease, there is no description regarding grain surface doping.

US Pat. No. 3,690,888 discloses a process for preparing silver halides containing polyvalent metal ions, the process comprising the step of making silver halides in the presence of protective colloids consisting primarily of acrylic polymers. ing.
It mentions in particular bismuth, iridium, lead and / or osmium ions as polyvalent metal ions, but there is no mention of hexacoordinated cyano complexes and grain surface doping.

Further, in these disclosed examples, it is not clearly shown that the ligand is incorporated into the lattice together with the transition metal, and the definition of the ligand of the transition metal complex compound and its effect are also described. Not listed.

On the other hand, European Patent Nos. 0336425 and 03
No. 36426, JP-A Nos. 2-20853 and 2-20854, disclose in the presence of hexacoordinated rhenium, ruthenium, osmium and iridium metal complexes having at least four cyan ligands. , A silver halide emulsion having excellent sensitivity and gradation stability over time and having improved low illumination failure is described. In addition, European patent 0
No. 336427 and JP-A-2-20852, hexacoordinate vanadium, chrome, manganese, iron, ruthenium containing nitrosyl or thionitrosyl ligands,
Emulsions have been disclosed in which the sensitivity is controlled by osmium, rhenium and iridium metal complexes to improve the low light reciprocity law failure. Further, in European Patent No. 0,336,689 and Japanese Patent Application Laid-Open No. 2-20855, a ligand of a hexacoordinated rhenium complex is a combination of halogen, nitrosyl, thionitrosyl, cyan, water and thiocyan. Disclosed are emulsions in which the sensitivity is controlled by a metal complex and the low light reciprocity law failure is improved. Furthermore, JP-A-3-11
In 8535, a transition metal complex in which one ligand of a hexacoordinated metal complex is carbonyl, and in JP-A 3-118536, transition in which two ligands of a hexacoordinated metal complex are oxygen. It is disclosed that an emulsion containing a metal complex inside is effective for photographic performance.

In these disclosed examples, 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, these disclosed examples relate to a technique of adding a transition metal complex during the precipitation of silver halide grains to dope into the bulk crystal of the grain, and the surface of the grain is doped with the transition metal complex. It was not limited to the technology to do. Further, usual gelatin is used as the protective colloid when the silver halide grains doped with the metal complex are formed. Regarding the interaction between metal and gelatin, T.H.J. James, Theory of Photographic Process, 4th Edition, Macmillan, Inc. (TH James,
"The Theory of the Photographic Process" 4th ed.
Macmillan), Chapter 2 (pp. 71-72). Noble metals such as gold and platinum, iridium and other heavy metals interact with gelatin to form complex salts,
It has been shown to 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.

[0014]

The object of the present invention is to improve the internal inefficiency due to the doping in the bulk crystal by surface-doping the silver halide grains with the transition metal complex, and to further improve the gelatin and the transition metal complex. By controlling the surface-doping of the transition metal complex by minimizing the interaction of the transition metal complex, the effect obtained by the surface doping of the transition metal complex is maximized.

[0015]

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. A silver halide photographic material characterized by being a silver halide emulsion chemically sensitized in the presence of a synthetic polymer compound having a protective colloid property and a hexacoordinate cyano complex; ) A silver halide photographic material according to (1) above, which has been chemically sensitized in the absence of gelatin; and (3) a minute halogenation prepared in the presence of a synthetic polymer compound having a protective colloid property. Achieved by the silver halide photographic material according to (1) or (2) above, wherein a part or all of nucleation and / or crystal growth of the silver halide emulsion is performed by supplying silver grains. .

As a result, by surface-doping the silver halide grains with hexacoordinated cyano complex ions, the internal inefficiency due to the dope in the bulk crystal is improved, and the hexacoordinated cyano complex salt interacts with gelatin. The unexpected adverse effects on photographic performance due to oxidation or reduction of transition metals, ligand exchange, decomposition, etc. are minimized, and the photographic performance of silver halide surface doping of hexacoordinate cyano complex ions is minimized. Was able to maximize the effect of.

The present invention will be described in more detail below. The hexacoordinate cyano complex salt used in the present invention has the following formula (I)
A salt containing a hexacoordinated transition metal complex ion satisfying the above condition. 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; and n is 3 or 4. This hexacoordinated metal complex salt dissociates when introduced into an aqueous medium, such as that used to form silver halide grains, so the counter cation has little importance. However, ammonium and alkali metal 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 present invention.

When the above hexacoordinated cyano complex ion is added during the precipitation of silver halide grains, it is incorporated into the silver halide grain crystals. 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, for example, silver bromide crystal can accommodate iodine ion larger than bromide ion, and further, cyano coordination of transition metal complex. A hexacoordinated cyano complex salt has seven covalent bonds within the silver halide crystal because the bond distance is reduced by the covalent bond between the ligand and the central transition metal, and the overall size of the transition metal complex is reduced. It can be understood that it is replaced with the vacancy ion of and is incorporated into the silver halide.

On the other hand, when the surface of the silver halide grains is surface-doped after the formation of the silver halide grains, a hexacoordinated cyano complex salt is added and aged, and the above idea can be applied as it is. That is, in this case, some or all of the hexacoordinated cyano complex salt substitutes for some lattice point ions on the grain surface to occupy lattice positions, or silver and / or halogen ions above the grain surface are It is considered that the hexacoordinate cyano complex ion replaces the lattice position to be occupied and chemisorbs to the particles. However, the details are unknown and we have to wait for future research.

The hexacoordinated cyano complex salt satisfying the requirements of the present invention can be added to the silver halide grains at the same concentration per mol of silver as conventionally used in the transition metal doping. . In this regard, a very wide range of densities are known, and it is known from JP-A-51-107129.
From the low concentration of 10 ^-10 mol per mol of silver disclosed in U.S. Pat. No. 3,876,676 and U.S. Pat.
No. 891 10 ⁻³ per mol of silver disclosed in each specification
Used in the high molar range. The effective concentration depends largely 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 ^-9 to 10 ^-4 mol per mol of silver. ,
Preferably 10 ⁻⁸ to 10 ⁻⁵ mol, more preferably 5 ×
It is 10 ⁻⁸ to 10 ⁻⁶ mol.

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 hydrogen ion concentration 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 as long as they are in the form of salts that can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts. it can.

The hexacoordinate cyano complex salt of the present invention is added in the chemical sensitization step. 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 sensitization of selenium, an unstable selenium compound is used, and Japanese Patent Publications Nos. 43-13489 and 44-157 are used.
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), selenoamides (eg, selenoacetamide, N, N-diethylphenylselenoamide), phosphine selenides (eg, triphenylphosphine selenide, penta) Fluorophenyltriphenylphosphine selenide), selenophosphates (for example, tri-p-tolylselenophosphate, 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.
The non-unstable selenium compounds described in Japanese Patent No. 4492, such as selenious acid, potassium selenocyanide, selenazoles, and selenides, can also be used.

In tellurium sensitization, an unstable tellurium compound is used, and Canadian Patent 800958 and British Patent 129 are used.
Nos. 5462 and 1396696, Japanese Patent Application No. 2
No. 333819, No. 3-53693, No. 3-131
Unstable tellurium compounds described in the respective specifications of No. 598 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 noble metal sensitization, 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 Japanese Patent No. 85 etc. 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, dimethylamineborane), 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, etc., but it is 10 ^-8 to 10 ⁸ 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 of the chemical sensitization in the 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. , And even 45-85
C is preferred.

As the synthetic polymer compound having a protective colloid action for silver halide grains used in the present invention, the following compounds are used.

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 polyvinyl alcohol, US Patent 300
No. 0741 of organic acid monoesters of polyvinyl alcohol, US Pat. No. 3,236,653, maleic acid esters of US Pat. No. 3,479,189.
A copolymer of polyvinyl alcohol and polyvinylpyrrolidone shown in the specification. 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 acrylate polymers shown in No. 1 and cyanoalkyl acrylates 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 it 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 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, gelatin may be additionally added in the steps of washing with water / desalting to chemical sensitization, but the content of gelatin is preferably at most 10 g / silver mole, and it is more preferable not to contain gelatin at all. preferable. However,
At the stage between the end of chemical sensitization and immediately before coating, silver halide is used as a vehicle (binder).
It is necessary to add 30 g or more, preferably 50 g or more per mol. For vehicles that can be used, RESEAE
The description of CH DISCLOSURE 176 volume Item 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 40 ° C to 8 ° C.
It is in the range of 0 ° C.

In the present invention, fine silver halide grains prepared in the presence of a synthetic polymer compound in which some or all of the nucleation and / or crystal growth of silver halide grains have a protective colloidal property are prepared. 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 an emulsion 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 vessel to which an emulsion containing fine silver halide grains is supplied is not particularly limited.
It is preferably 150 g or less, more preferably 80 g or less, and further preferably 20 g or less per mol of silver halide. 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 gelatin content is more preferably 10 g / silver mole or less, and it is more preferred that the gelatin is not contained at all. However, in the stage from the end of chemical sensitization to immediately before application,
It is necessary to add 30 g or more, preferably 50 g or more, per 1 mol of silver halide, using gelatin as a vehicle (binder). For available vehicles, see RE
SEAECH DISCLOSURE Volume 176 Item 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 40 ° C.
It is in the range of -80 ° C. The temperature during the formation of fine silver halide grains is 40 ° C. or lower, preferably 3
It is 5 ° 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 adversely affect. 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 grain according to the present invention has a regular crystal form (normal grain) such as hexahedron, octahedron, dodecahedron, tetradecahedron, icosahedron and 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.

The silver halide emulsion used in the present invention can be produced by any method known so far. 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 the simultaneous mixing method, 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 can be used. Further, British Patent No. 1535016, Japanese Patent Publication Nos. 48-36890 and 52-1636.
No. 4, etc., a method of changing the addition rate of silver nitrate or an alkali halide aqueous solution according to the particle growth rate, US Pat. No. 4,242,445,
It is preferable to grow rapidly within a range not exceeding the critical degree of supersaturation by using a method of changing the concentration of the aqueous solution as described in JP-A-55-158124. These methods are preferably used because re-nucleation does not occur and silver halide grains grow uniformly.

Instead of adding the silver salt solution and the halogen salt solution to the reaction vessel, finely prepared fine particles are added to the reaction vessel to cause nucleation and / or grain growth to obtain silver halide grains. It is preferred to use the method. Regarding this technique, JP-A-1-183644, JP-A-1-183645, and US Pat.
08, JP-A-2-44335, JP-A-2-4
3534 and JP-A-2-43535. According to this method, the distribution of halogen ions in the crystal of emulsion grains can be made uniform, and favorable photographic characteristics can be obtained.

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 as described above but also a grain having a so-called junction structure can be prepared. Examples of these are JP-A-59-133540 and JP-A-5-135540.
No. 8-108526, European Patent 199290A2
Japanese Patent Publication No. 58-24772 and Japanese Patent Laid-Open No. 59-72
-16254.

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 with each other, but a silver salt compound not having a rock salt structure such as silver rhodan or 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 portion is high and the silver iodide content of the shell portion 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 and the like; 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 benzoterazole nucleus and the like can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

For the merocyanine dye or the composite 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 the 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 and stilbene derivatives described in JP-B-59-18691, and JP-B-49-46932. 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, etc. Is mentioned.

The sensitizing dye is added after chemical ripening or before chemical ripening. For the silver halide grains of the present invention,
Most preferably, the sensitizing dye is added during chemical ripening or before chemical ripening (for example, during grain formation or physical ripening).

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, during storage or during 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 the chemical sensitization, but more preferably during the chemical ripening or before the start of the chemical ripening. it can.

The emulsion of the present invention has one emulsion layer or two emulsion layers.
It can be used for a photographic light-sensitive material having an arbitrary layer structure, regardless of whether it has more layers. The silver halide multilayer color photographic light-sensitive material using the emulsion of the present invention has a multilayer 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, and other light-sensitive materials may be used regardless of whether they have one emulsion layer or multiple layers, such as X-ray light-sensitive materials, 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 of the silver halide emulsion of the present invention, for example, binder, chemical sensitizer, spectral sensitizer, stabilizer, gelatin hardening agent, surfactant, antistatic agent, polymer latex, matting agent. , 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.

The description of these Research Disclosures is 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 color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor with a coupling reaction or a coupler which releases a development accelerator 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 coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type couplers, 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 preferable and US Pat. No. 4,540 from the viewpoint of low yellow sub-absorption of the coloring dye and light fastness. , 650, pyrazolo [1,
5-b] [1,2,4] triazole is particularly preferred.

The cyan couplers which can be used in the present invention include oil-protection type naphthol type and phenol type couplers. The naphthol type couplers described in US Pat. No. 2,474,293, etc., preferably US Pat. Nos. 4146396 and 422
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in the specifications of Nos. 8233 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. As such couplers, specific examples of magenta couplers can be found in U.S. Pat. No. 4,366,237 and British Patent 2,125,570, and European Patent 96570 and West German Application 32.
In each specification of No. 34533, specific examples of yellow, magenta or cyan couplers are described.

The present invention may include a so-called DIR coupler which releases a development inhibitor upon development. 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. 59-90438 and Japanese Patent Application No. 59-39653.
It is a reactive DIR coupler described in Japanese Patent Laid-Open Publication No. 1994-242242.

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 the gelatin hardening agent 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 usually 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 developing solution and black and white developing solution
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 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 subjected to a washing and / or stabilizing step after desilvering. 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).

[0086]

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: Silver bromide octahedron emulsion using gelatin" 866
To cc water, 36 g gelatin and 0.25 g potassium bromide were added and dissolved, 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 36 cc of 0.088 M potassium bromide aqueous solution (solution 2) were added in 10 minutes, and subsequently 176 cc of solution 1 and solution 2 were added in 7 minutes by a usual double jet method. After adding an additional 1.4 g of potassium bromide,
1010 cc of 0.82 M silver nitrate aqueous solution (solution 3)
Initially, the flow rate was accelerated from a flow rate of 1.8 cc / min to be added in 78 minutes, and at the same time, a 0.90 M potassium bromide aqueous solution (solution 4) was controlled so as to be maintained at a silver potential of 0 mV (vs. saturated calomel electrode). Added. Furthermore, 0.51
M silver nitrate aqueous solution (solution 5) was added at 578 cc and 0.51M.
578 cc of aqueous potassium bromide solution (solution 6) was added over 24 minutes at a constant flow rate. After the addition was completed, the temperature was lowered to 35 ° C., the soluble salts were removed by a precipitating method on the way, and then the temperature was brought to 40 ° C. again to further add and dissolve the gelatin to obtain pH 6.
Adjusted to 3. The obtained grains were monodisperse silver bromide octahedral grains (variation coefficient: 10%) having a projected area diameter of 0.8 μm.

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

[0088]

[Chemical 1]

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

"Chemically sensitized Emulsion A-1" (Comparative Example) Emulsion A was heated to 60 ° C. and sodium thiosulfate was added to 1.2.
× 10 ^-5 mol / mol silver was added, and after 1 minute, potassium chloroaurate was added at 3.6 × 10 ^-6 mol / mol silver and potassium thiocyanate at 5.1 × 10 ^-4 mol / mol silver. The emulsion was optimally chemically sensitized to give Emulsion A-1.

“Chemically Sensitized Emulsions A-2 to A-5” (Comparative Example) In Emulsion A-1, 20 minutes before the addition of sodium thiosulfate,
Each of the following (2), (3), (4) and (5)
Emulsion A-1 except that ^{x10 -5} mol / mol silver was added.
Emulsions 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 ]

"Chemically sensitized Emulsion B-1" (Comparative Example) Emulsion B was heated to 60 ° C. and sodium thiosulfate was added to 1.2.
× 10 ^-5 mol / mol silver was added, and after 1 minute, potassium chloroaurate was added at 3.6 × 10 ^-6 mol / mol silver and potassium thiocyanate at 5.1 × 10 ^-4 mol / mol silver. The emulsion was optimally chemically sensitized to give Emulsion B-1. After the chemical sensitization, gelatin was added as a coating binder.

“Chemically Sensitized Emulsions B-2 to B-5” (Invention) In Emulsion B-1, 20 minutes before the addition of sodium thiosulfate,
1 × 1 each of (2), (3), (4) and (5)
Emulsions B-2, B-3, B-4 and B-5 obtained in exactly the same manner as Emulsion B-1, except that 0 ^-5 mol / mol silver was added. After the chemical sensitization, gelatin was added as a coating binder. Then Emulsion A-1,
B-1, A-2, A-3, A-4, A-5, B-2, B
-3, B-4 and B-5 emulsions were coated at a silver amount of ² g / m ² . The obtained coating samples are coated samples A-1, B-
1, A-2, A-3, A-4, A-5, B-2, B-
3, B-4 and B-5. Further, the spectral sensitizing dye shown in (6) below was added to the above emulsion at 2.5 × just before coating.
10 ⁻⁴ mol / mol silver was added and adsorbed on silver halide grains at 40 ° C. for 20 minutes.

[0098]

[Chemical 2]

The above emulsion was similarly coated 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 exposed to blue light by an EG & G sensitometer for 10 ^-3 seconds and then developed. The following MAA-1 developer was used as the developer, and the development was carried out at 20 ° C. for 10 minutes.

──────────────────────────────────── 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.

[0102]

[Table 1] Table 1 ──────────────────────────────────── Emulsion protection Six cyano Relative blue floor Tone-specific desensitization width (* 3) Colloidal complex salt 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 K ₄ [Fe (CN ) ₆ ] 40 1.7-0.45 Comparative Example A-3 Gelatin K ₃ [Fe (CN) ₆ ] 35 1.8-0.48 Comparative Example A-4 Gelatin K ₄ [Ru (CN) ₆ ] 55 1.8-0.45 Comparative Example A-5 Gelatin K ₃ [Ir (CN) ₆ ] 60 1.7-0.40 Comparative Example B-2 (1) K ₄ [Fe (CN) ₆ ] 125 2. 0-0.28 Invention B-3 (1) K ₃ [Fe (CN) ₆ ] 115 1.9-0.25 Invention B-4 (1) K ₄ [Ru (CN) ₆ ] 125 2. 0-0 19 invention _{B-5 (1) K 3} [Ir (CN) 6] 115 2.1 -0.20 present invention ────────────────────── ────────────── (* 1) Spectral sensitizing dye blank coating samples A-1 to B
A relative value of the reciprocal of the exposure amount giving a fog + a density of −5. (* 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 apparent from Table 1 that emulsions chemically sensitized by coexisting gelatin and a hexacoordinate cyano complex salt have a remarkable 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 invention is
High intrinsic sensitivity and high contrast at high illuminance, and intrinsic desensitization by the spectral sensitizing dye is remarkably improved.

Example 2 "Emulsion C: Octahedral Emulsion Using Gelatin" In Emulsion A, 1% by weight of gelatin was added to Solution 2, Solution 4 and Solution 6, and Solution 1, Solution 2 and Solution 3 were added. , Solution 4, solution 5 and solution 6 are introduced into a mixer installed outside the reaction vessel, and 1% by weight gelatin aqueous solution as solution 7 is simultaneously introduced into the above mixer as a third solution. It was prepared in the same manner as Emulsion A, except that a fine silver halide emulsion was fed into the reaction vessel.

"Emulsion D: Octahedral silver bromide emulsion using synthetic compound having protective colloid property" Instead of the gelatin of Emulsion C, synthetic protective colloid represented by the following (7) is added in an amount of 2 g in a reaction vessel, Were prepared in the same manner as Emulsion C except that 0.1 wt% was used in Solution 2, Solution 4, Solution 6 and Solution 7.

[0106]

[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.

"Chemically sensitized Emulsion C-1" (Comparative Example) Emulsion C was heated to 60 ° C. and sodium thiosulfate was added to 1.2.
× 10 ^-5 mol / mol silver was added, and after 1 minute, potassium chloroaurate was added at 3.6 × 10 ^-6 mol / mol silver and potassium thiocyanate at 5.1 × 10 ^-4 mol / mol silver. The emulsion was optimally chemically sensitized to give Emulsion C-1.

“Chemically Sensitized Emulsions C-2 to C-5” (Comparative Example) In Emulsion C-1, 20 minutes before the addition of sodium thiosulfate,
1 × 1 each of (2), (4), (8) and (9)
0 except ^-5 mol / mol Ag added with it, to prepare an emulsion obtained in the same manner as Emulsion C-1, the C-2, C-3, C-4 and C-5.

(8) K ₃ [Co (CN) ₆ ]

(9) K ₄ [Re (CN) ₆ ]

"Chemically Sensitized Emulsion D-1" (Comparative Example) Emulsion D was heated to 60 ° C. and sodium thiosulfate was added to 1.2.
× 10 ^-5 mol / mol silver was added, and after 1 minute, potassium chloroaurate was added at 3.6 × 10 ^-6 mol / mol silver and potassium thiocyanate at 5.1 × 10 ^-4 mol / mol silver. The emulsion was optimally chemically sensitized to give Emulsion D-1. After the chemical sensitization, gelatin was added as a coating binder.

“Chemically Sensitized Emulsions D-2 to D-5” (Invention) In Emulsion D-1, 20 minutes before the addition of sodium thiosulfate,
1 × 1 each of (2), (4), (8) and (9)
Emulsions D-2, D-3, D-4 and D-5 obtained in exactly the same manner as Emulsion D-1, except that 0 ^-5 mol / mol silver was added. After the chemical sensitization, gelatin was added as a coating binder.

Immediately before coating, the spectral sensitizing dye shown in (6) was added to the above emulsion in an amount of 2.5 × 10 ⁻⁴ mol / mol silver and adsorbed on silver halide grains at 40 ° C. for 20 minutes. It was The above emulsion was coated in the same manner with a silver amount of ² g / m ² . The obtained coating 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.

[0116]

[Table 2] Table 2 ──────────────────────────────────── Emulsion protection Six cyano Relative blue floor Tone-specific desensitization width (* 3) Colloidal complex salt Sensitivity (* 1) (* 2) ΔlogE Reference ──────────────────────────── ───────── C-1 Gelatin-100-100-0.67 Comparative Example D-1 (7) -85 1.3-0.60 Comparative Example C-2 Gelatin K ₄ [Fe (CN ) ₆ ] 40 1.7-0.45 Comparative Example C-3 Gelatin K ₄ [Ru (CN) ₆ ] 55 1.8-0.45 Comparative Example C-4 Gelatin K ₃ [Co (CN) ₆ ] 60 1.9-0.46 Comparative Example C-5 Gelatin K ₄ [Re (CN) ₆ ] 65 1.7-0.40 Comparative Example D-2 (7) K ₄ [Fe (CN) ₆ ] 125 2. 0-0.28 Invention D-3 (7) K ₄ [Ru (CN) ₆ ] 125 2.0-0.19 Invention D-4 (7) K ₃ [Co (CN) ₆ ] 120 2. 1-0 25 invention _{D-5 (7) K 4} [Re (CN) 6] 130 2.0 -0.20 present invention ────────────────────── ──────────────

(* 1) Relative value of the reciprocal of the exposure amount giving a fog + density of 0.1 for 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 apparent from Table 2 that emulsions chemically sensitized in the presence of gelatin and a hexacoordinated cyano complex salt 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 invention is
High intrinsic sensitivity and high contrast at high illuminance, and 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 / mol of silver or less of gelatin. A silver halide photographic material, which is a silver halide emulsion chemically sensitized in the presence of a compound and a hexacoordinate cyano complex. 2. The silver halide photographic material according to claim 1, which is chemically sensitized 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.