JP3262394B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a photographic light-sensitive material. Specifically, it is a silver halide photographic material having improved reciprocity failure, high contrast, low intrinsic desensitization due to addition of a spectral sensitizing dye, and excellent spectral sensitivity.

[0002]

2. Description of the Related Art In silver halide photographic materials, one of the means for achieving high sensitivity and high image quality is a technique of doping a metal complex salt containing a metal ion or a ligand into silver halide grains. is there. This doping technique is intended to improve the characteristics of silver halide grains, thereby improving the characteristics of the whole emulsion and achieving high sensitivity and high image quality.

[0003] Regarding this doping technique, research
Disclosure (Research Disclosure), 176,
17643 (1978), section IA, describes metal complex salts that can be introduced during grain formation.

A technique for doping a metal complex with a complex salt is described in US Pat. No. 2,448,060 by Trivelli and Smith. At this time, the metal complex salt is represented by the general formula R ₂ MX ₆ (where R represents hydrogen, an alkali metal or an ammonium group, and M represents a transition metal of the platinum group except osmium, for example, platinum, palladium, iridium, rhodium, Represents ruthenium, and X represents a halogen atom, for example, chlorine or bromine.) Although these metal complex salts are water-soluble and have an effect as an antifoggant and a stabilizer when introduced, they disclose that they can be sensitized when a palladium (IV valent) hexacoordinate metal complex salt is added. The time of introduction is at any stage before or during precipitation of silver halide, before or during first ripening (physical ripening), or before or during second ripening (chemical ripening). States that

Several patents are known for metal complex salt dopants containing cyanide ions. U.S. Pat. Nos. 3,790,390 disclose simple salts of fourth period elements such as iron, cobalt and nickel as well as hexacoordinate metal complex salts containing cyano ligands, ruthenium and rhodium by forming stable compounds. , Palladium, osmium, iridium, or the use of hexacoordinate metal complexes containing only halide ligands. here,
There is a description of a silver halide emulsion containing a hexacyano complex of iron (II), iron (III), and cobalt (III). EP 0,242,290 comprises silver halide grains formed in the presence of one or more complex salts of rhodium (III) with 3, 4, 5 or 6 cyano ligands. In silver halide emulsions, a reduction in high intensity failure has been disclosed. In these disclosure examples, it was clearly shown that the metal ion containing the ligand was taken into the particles, and the effect of including the ligand of the metal complex salt was not described.

JP-A-2-20853, JP-A-2-20
No. 854 describes a silver halide emulsion formed in the presence of a rhenium, ruthenium, osmium, or iridium complex salt having at least four cyano ligands. The effect is particularly excellent in sensitivity and gradation stability with time, and low illuminance failure is improved.

Further, Japanese Patent Application Laid-Open Nos. Hei.
-20855, JP-A-3-118535, JP-A-3
No. 118536 discloses that NO, NS, CO, which are effective ligands as one of the bridging ligands of a cyano ligand,
(O) describes that it can be used in combination with a ligand such as ₂ .

In these disclosures, the concept of doping the hexacoordinate metal complex by replacing it with seven vacancies of one silver ion and six adjacent halide ions inside the crystal is proposed. This is different from the conventional view that metal ions simply replace silver ions.

As mentioned above, cyano metal complex salts have shown excellent performance. In particular, hexacyano metal complex salts are known as stable compounds and are important compounds in photographic performance.

The metal doping technique was initially focused on the discovery and search for new dopants.
No. 0 contains a photographic silver halide emulsion in which the region containing iridium ions is limited to a distance from about 1 × 10 ⁻⁷ cm below the grain surface to about 20% of the grain radius, or on the grain surface. Disclosed is a method of preparing a photographic silver halide emulsion which comprises stopping the addition of iridium ions long before stopping the silver salt addition so that substantially no iridium ions remain. However, there is no description of the hexacyano metal complex here.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a hexacyano metal complex containing a cyan ion having a high photographic effect as a ligand when doped with a hexacyano metal complex. To provide a silver halide light-sensitive material having good stability.

[0012]

The above objects have been attained by the following. 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a hexacyano metal complex salt, is gold-sensitized, and is gold- sensitized. A silver halide photographic light-sensitive material comprising an emulsion which has been washed with an aqueous solution of a halide salt having a concentration of 10 ^-4 M or more prior to applying. 2. The aqueous halide salt solution is used as an emulsion halide.
Characterized in that it is the same halide salt aqueous solution as
1. The silver halide photographic light-sensitive material as described above.

Hereinafter, the present invention will be described in detail. The halide salts used when washing the emulsion are chloride, bromide and iodide salts, and any water-soluble salts may be used. More preferably, they are the same chloride, bromide and iodide as the halogen composition of the emulsion. At this time, the counter cation is preferably an alkali metal or ammonium ion. The concentration of the halide salt is a 10 ^-4 M or more, preferably 10 ^-1 to 10 ^-4 M, more preferably 10 ^-1 to 10
^-3 M. Here, M represents a molar concentration and can be written as mol / dm ³ .

The time for washing the doped emulsion is before chemical sensitization after grain formation, preferably before noble metal sensitization such as gold sensitization. The cleaning method is
The method is to add the halide salt directly or by dissolving it in a solvent in which the salt is soluble, and preferably to add an aqueous solution in which the salt is dissolved.

As described in the prior art, among the metal complex salts, the cyano metal complex salt shows excellent performance. In particular, hexacyano metal complex salts are known as more stable compounds and are important compounds in photographic performance.

By washing the hexacyano metal complex salt-doped emulsion with a high-concentration halide salt, unnecessary compounds on the surface of silver halide grains and in a medium such as gelatin can be removed. Thereby, a better photographic effect was obtained.

The hexacyano metal complex used in the present invention is a salt containing a six-coordinate transition metal complex satisfying the following general formula (I). In the general formula (I) [M (CN) ₆ ] ^{n -where} , M is the fourth, fifth and sixth period of the periodic table of elements, and is a fifth, sixth or seventh group of the periodic table. , 8th, 9th
A transition metal consisting of group 10 and group 10, more preferably iron, ruthenium, osmium, cobalt, rhodium, iridium, rhenium, chromium, and n is 3,
4 or 5. At this time, since these hexacyano metal complex salts are present in the form of ions in the aqueous solution, the counter cation is not important, but alkali metal ions and ammonium ions suitable for the precipitation operation of the silver halide emulsion are more preferable.

The compound of the present invention is dissolved in water or a mixed solvent with a suitable water-miscible organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). Can be added.

The amount of the metal complex salt of the present invention varies depending on the composition of the silver halide grains to be used, but is generally 10 ^-10 to 10 ^-2 mol per mol of silver halide, preferably ¹⁰ to 10 ^-2 mol per mol of silver halide. ^{About -7} to 10 ^-3 mol is used.

The doping amount and doping ratio of the hexacyano metal complex salt in the silver halide grains can be determined by the atomic absorption method, the ICP method (Inductively
Coupled Plasma Spectrometry; ICPMS (Inductively Coup)
Led plasma mass spectrometry (inductively coupled plasma mass spectrometry) or the like.

The hexacyano metal complex salt used in the present invention may be arbitrarily added at the doping position during the preparation of silver halide grains, that is, at a part or all of nucleation and / or crystal growth. . More preferably, it is near the grain surface of the silver halide grains, and at that time, it is preferable to dope at 10 ^-5 mol / mol silver or more.

The hexacyano metal complex salt used in the present invention may be added directly to the reaction solution when forming silver halide grains,
It is preferable that the silver halide grains are contained by adding them to an aqueous halide solution for forming silver halide grains or other solutions to form grains. It is also preferable to add and dissolve silver halide grains containing a metal complex salt in advance, and deposit the solution on another silver halide grain to contain these metal complex salts. Furthermore, various addition methods can be combined.

The concentration of hydrogen ions in the reaction mixture when adding the hexacyano metal complex used in the present invention is not particularly limited, but is preferably pH 3 or more.

Supplying a silver halide emulsion containing fine silver halide grains prepared in the presence of a synthetic polymer compound having a protective colloid property in part or all of silver halide grain formation and / or crystal growth. In such a case, the hexacyano metal complex salt may be doped into fine silver halide grains, or may be supplied alone into the reaction vessel.

The hexacyano metal complex salt used in the present invention can be used alone or in combination of two or more.
In addition, other lead, typical metal ions such as cadmium, cerium, lanthanide metal ions such as europium, or six-coordinate, four-coordinate transition metal complex salt, palladium, platinum,
It can be used in combination with a two-coordinate transition metal complex salt such as silver or gold. At this time, the counter ion is preferably an alkali metal ion, an alkaline earth metal ion, an ammonium ion, an acetate ion, a nitrate ion, a sulfate ion, a phosphate ion, or a hydroxyl ion.

The silver halide emulsion used in the present invention comprises:
Any of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride may be used.

The size of the silver halide grains used in the present invention is not particularly limited, but may be from 0.05 μm to 10 μm.
m, preferably 0.1 μm to 3 μm. The size of the silver halide grains used in the present invention depends on the temperature and pAg.
It can be prepared by controlling, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth.

Examples of frequently used silver halide solvents include thiocyanates, thioethers, thioureas and the like, and ammonia can be used in combination as long as no adverse effect is caused. For example, thiocyanates (U.S. Pat. Nos. 2,222,264 and 2,44)
Nos. 8,534, 3,320,069) and thioether compounds (U.S. Pat. Nos. 3,271,157, 3,574,628, 3,704,130, and 4). 297,439, 4,276,347), thione compounds (JP-A-53-144319, 53-82408, 55-77737, etc.) and amine compounds (JP-A-54-100717). No. etc.) can be used.

The silver halide grains according to the present invention may have a regular crystal system (normal crystal grains) such as hexahedron, octahedron, dodecahedron, tetrahedron, dihedron, and forty-octahedron. The particles may be irregular, such as spherical or potato-like crystals, and may be particles of various shapes having one or more twin planes. The silver halide emulsion used in the present invention has a thickness of 0.5 μm or less, preferably 0.3 μm or less and a diameter of preferably 0.6 μm or more,
Particles with an average aspect ratio of 3 or more account for 50% of the total projected area
Tabular grain emulsions occupying the above are also preferred. The silver halide emulsion used in the present invention has a statistical coefficient of variation (a value S / d obtained by dividing the standard deviation S by the diameter d in the distribution expressed by the diameter when the projected area is approximated by a circle) is 20. %
The following monodisperse emulsions are particularly preferred. Also,
Two or more emulsions may be mixed.

The silver halide emulsion used in the present invention can be produced by any of the methods known so far. That is, a silver salt aqueous solution and a halide aqueous solution are added to a reaction vessel having an aqueous gelatin solution with efficient stirring. As a concrete method, Chimie er Physique Photographeque by P. Glafkides
(Paul Montell, 1967), GF Duffin, Photographic Emulsion Chemistry
istry) (Focal Press, 1966), Buoy
Making and Coating Photographic Emulsion by VL Zelikman et al.
(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 a method of reacting a soluble silver salt with a soluble halide may be any of a one-side mixing method, a double-mixing method, a combination thereof, and the like. . As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a controlled double jet method can be used. Also, British Patent No. 1,535,016
JP-A-48-36890, JP-B-52-16364, and the like, a method in which the addition rate of silver nitrate or an aqueous alkali halide solution is changed according to the grain formation rate, and US Pat. 445, JP-A-55
It is preferred that the growth be carried out quickly within a range not exceeding the critical supersaturation using a method of changing the concentration of the aqueous solution as described in -158124 or the like. These methods are preferably used because silver halide grains grow uniformly without causing renucleation.

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

Further, in the present invention, emulsion grains having various structures can be used. So-called double-structured particles composed of the inner part (core part) and the outer part (shell part) of the particles, further, triple-structured particles as disclosed in JP-A-60-222844, and multi-layered particles having more than that are used. In order to provide a structure inside the emulsion grains, not only the above-described wrapping structure but also a grain having a so-called junction structure can be produced. These examples are described in JP-A-58-1.
08526, 59-133540, European Patent No. 1
No. 99290A2, JP-B-58-24772, JP-A-59-16254 and the like. 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 when the host crystal is uniform in halogen composition. In the case of a joint structure, a combination of silver halides is naturally possible, but a silver chloride having a non-rock salt structure such as silver rhodanate and silver carbonate can be combined with silver halide to form a joint structure. A non-silver salt compound such as PbO may be used as long as it can form a junction structure. In the case of silver iodobromide particles having these structures, for example, in core-shell type particles, the core portion may have a high silver iodide content and the shell portion may be high. Similarly, grains having a bonding structure may be grains having a high silver iodide content of the host crystal and relatively low silver iodide content of the bonding crystal, or vice versa. In addition, the boundary portion having a different halogen composition of the grains having these structures may be a clear boundary, or may be an unclear boundary formed by a mixed crystal due to a composition difference. It may have a structural change. The silver halide emulsion for use in the present invention is a process for imparting roundness to grains as disclosed in European Patents 0096727B1 and 0064412B1.
Alternatively, DE 2306447C2, JP-A-60-2
Surface modification as disclosed in US Pat. No. 21,320 may be performed. The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but an internal latent image type emulsion may be used by selecting a developing solution or development conditions as disclosed in JP-A-59-133542. Can be. Further, a shallow internal latent image type emulsion covered with a thin shell can be used according to the purpose.

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

For use in the emulsion layer or intermediate layer of the light-sensitive material of the present invention
Binders or protective colloids that can be
It is advantageous to use ratine, but other hydrophilic
Lloyd can also be used. For example, gelatin derivatives,
Graft polymer of gelatin and other polymers, albumi
Proteins such as casein and casein; hydroxyethyl cellulose
, Carboxymethylcellulose, cellulose sulfate
Cellulose derivatives such as ters, sodium alginate,
Sugar derivatives such as starch derivatives; polyvinyl alcohol,
Rivinyl alcohol partial acetal, poly-N-vinyl
Pyrrolidone, polyacrylic acid, polymethacrylic acid, poly
Acrylamide, polyvinyl imidazole, polyvinyl
Various syntheses such as mono- or copolymers such as pyrazole
A hydrophilic polymer substance can be used. Gelatin
In addition to general-purpose lime-processed gelatin, acid-processed gelatin and
Journal of the Japan Society of Scientific Photography (Bull. Soc. Phot. Japan),1
6, 30 (1966).
May be used, or a hydrolyzate of gelatin may be used.
Can be

In the light-sensitive material of the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. For example, chromium salts, aldehyde salts (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.) are specific examples. Active halides (such as 2,4-dichloro-6-hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2- Bis (vinylsulfonylacetamide) ethane, bis (vinylsulfonylmethyl) ether or a vinyl-based polymer having a vinylsulfone group in a side chain are preferred because they can quickly cure a hydrophilic colloid such as gelatin and provide stable photographic properties. N-carbamoylpyridinium salts ((1-
Morpholinocarbonyl-3-pyridinio) methanesulfonate and the like and haloamidinium salts (such as 1- (1-chloro-1-pyridinmethylene) pyrrolidinium-2-naphthalenesulfate) also have fast and excellent curing rates.

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

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

In the present invention, sulfur sensitization, selenium sensitization,
Tellurium sensitization, noble metal sensitization and reduction sensitization can be used in conjunction gold sensitization and set <br/>.

In the sulfur sensitization, there is a sulfur sensitization method using a so-called unstable sulfur compound capable of producing silver sulfide by reacting with silver ions. Specifically, P. Grafkides, Chim.
ie et Physique Photographique (Paul Montel,
1987, 5th edition), Research Disclosure, 307, 307105.
No., edited by TH James, The Theory of the Photograph
ic Process (published by Macmillan, 1977, 4th edition),
H. Frieser, Die Grundlagender Photographischen P
rozess mit Silver-halogeniden (Akademische Verlag
sgeselbshaft, 1968). Specific examples of the sulfur sensitizer include thiosulfates (eg, sodium thiosulfate, p-toluenethiosulfonate, etc.), thioureas (eg, allylthiourea, N, N ′).
-Diphenylthiourea, triethylthiourea, acetylthiourea, N-ethyl-N '-(4-methyl-2-thiazolyl) thiourea, etc.), thioamides (eg, thioacetamide, N-phenylthioacetamide, etc.), rhodanine (Eg, rhodanine, N-ethyl rhodanine, 5-benzylidene rhodanine, 5-benzylidene-
N-ethyl-rhodanine, diethyl rhodanine, etc.), as well as thiohydantoins,
Oxo-oxazolidine-2-thiones, dipolysulfides, thiosulfonic acids, mercapto compounds such as cysteine, polythionates, elemental sulfur, sodium sulfide and the like can be used.

In the selenium sensitization, known unstable selenium compounds, specifically, colloidal metal selenium, JP-B-44-15748 and JP-B-43-1348 can be used.
No. 9, Japanese Patent Application No. 2-130976, 2-229300
No. 2-272879, No. 3-53693, No. 3
Compounds described in JP-A-82929 and the like are shown. More specifically, selenoureas (for example, aliphatic selenoureas such as selenourea, N, N-dimethylselenourea, N, N-diethylselenourea, tetramethylselenourea; N, N, N′-) Trimethyl-N'-acetylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, NN'-trimethyl-N'-4-chlorophenylcarbonylselenourea, N, N, N Substituted selenoureas such as'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc.), selenoamides (eg, selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, bis- (adamantyl) selenoketone, etc.), isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenocarboxylic acids and esters (For example,
Selenopropionic acid, methyl-3-selenobutyrate, etc., selenides (eg, dimethyl selenide, diethyl selenide, triphenylphosphine selenide, etc.), selenophosphates (eg, tri-p
-Tolyl selenophosphate), colloidal metal selenium and the like.

As for tellurium sensitizers, US Pat.
623,499, 3,320,069, 3,7
72,031; British Patent No. 235,211;
121,496, 1,295,462, 1,3
96,696; Canadian Patent No. 800,958; Journal of Chemical Society Chemicals.
Communication (J. Chem. Soc., Chem. Commun.)
635 (1980), 1102 (1979), 64
5 (1979), Journal of Chemical Society Parkinson Transaction (J. Chem.
Soc., Perkin. Trans.) 1 , 2191 (1980), and Japanese Patent Application Nos. 2-333819 and 3-131598. More specifically,
Colloidal tellurium, telluroureas (e.g., allyl tellurourea, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N ', N'-dimethyltellurourea, N, N'-dimethylethylenetellurourea,
N, N′-diphenylethylene tellurourea), isotellurocyanates (eg, allyl isotellurocyanate), tellurokenes (eg, telluroacetone, telluroacetophenone), telluramides (eg, telluroacetamide, N, N-dimethyltellurobenzamide), Tellurohydrazide (eg, N, N ′, N′-trimethyltellurobenzhydrazide), telluroester (eg, t-
Butyl-t-hexyl telluride ester), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride),
Other tellurium compounds (eg, British Patent No. 1,295,46)
No. 2, negatively-charged telluride ion-containing gelatin, potassium telluride, potassium tellurocyanate, sodium salt of telluropentathionate, allyl tellurocyanate, and the like can be used.

In noble metal sensitization, the above-mentioned P. Grafkid
es, Chimie et Physique Photographique (Paul Mon
tel, 1987, 5th edition), Research Disclosure, 307, 307
Noble metal sensitizers such as gold, platinum, palladium, and iridium described in No. 105 and the like can be used in combination.
In this case, in combination with the gold sensitizer, more specifically, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, in addition to gold selenide U.S. Patent No. 2,642,361, the first Gold compounds described in 5,049,484, 5,049,485 and the like can be used.

In reduction sensitization, the above-mentioned P. Grafkides
Written by Chimie et Physique Photographique (Paul Mont
el company, 1987, 5th edition), Research Disclosure, 307, 3071
Known reducing compounds described in No. 05 or the like can be used. Specifically, aminoiminomethanesulfinic acid (also called thiourea dioxide), borane compound (for example, dimethylamine borane), hydrazine compound (for example, hydrazine, p-tolylhydrazine), polyamine compound (for example, diethylenetriamine, triethylene Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas, and the like.

The combination of these chemical sensitization mosquito Rukogen sensitization and gold sensitization is preferred. The 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 silver halide grains used, chemical sensitization conditions, and the like.
10 ^-8 to 10 ^-2 mol, preferably 10 ^{-7 to} 5 per mol
About ^10-3 mol is used. The amount of the noble metal sensitizer used in the present invention is 10 ⁻⁷ to 1 mol per mol of silver halide.
About 10 ^-2 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pAg is 6 to 1
1, preferably 7 to 10 and a pH of 4 to 1
0, the temperature is 40 to 95 ° C, preferably 45 to 85
° C.

The silver halide photographic emulsion used in the present technology contains various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing the photographic performance. It can be contained. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, and aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes ; Benzenethiosulfonate, benzene sulfinic acid, known as antifoggants or stabilizers such as benzenesulfonic acid amide, can be added to many compounds.

The light-sensitive material of the present invention comprises a coating aid, an antistatic
One or more surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (eg, development acceleration, high contrast, sensitization).

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in a water-impregnated colloid layer as a filter dye or for the purpose of preventing irradiation or halation or other various purposes. As such dyes, oxonol dyes, hemioxonol dyes,
Styryl dyes, merocyanine dyes, anthraquinone dyes and azo dyes are preferably used. In addition, cyanine dyes, azomethine dyes, triarylmethane dyes and phthalocyanine dyes are also useful. The oil-soluble dye may be emulsified by an oil-in-water suitable dispersion method and added to the water-penetrating colloid layer.

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

Various color couplers can be used in the photographic material of the present invention, and specific examples thereof are described in Research Disclosure (RD) No. 17643, VI
It is described in the patents described in IC to G. As the yellow coupler, for example, US Pat.
No. 01, No. 4, 022, 620, No. 4, 326,
No. 024, No. 4, 401, 752, Japanese Patent Publication No. 58-1
No. 0739, British Patent Nos. 1,425,020 and 1,476,760 are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable. For example, US Pat. Nos. 4,310,619 and 4,351,8
No. 97, EP 73,636, U.S. Pat.
No. 61, 432, No. 3, 725, 067, Research Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Patent No. 4,500,630
No. 4,540,654 are preferred.
Cyan couplers include phenolic and naphthol couplers, for example, US Pat. No. 4,052,
No. 212, No. 4, 146, 396, No. 4, 22
Nos. 8,233, 4,296,200, 2,3
No. 69, 929, No. 2, 801, 171, No. 2,
No. 772, 162, No. 2, 895, 826, No. 3, 772, 002, No. 3, 758, 309, No. 4, 334, 011, No. 4, 327, 173,
West German Patent Publication No. 3,329,729, European Patent No. 12
No. 1,365A, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559,
No. 4,427,767, European Patent No. 161,626
Those described in No. A are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in, for example, Research Disclosure No. No. 17643, Section VII-G, U.S. Pat.
63,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,926, 4,138,258,
Those described in British Patent No. 1,146,368 are preferred.

Examples of couplers in which the color forming dye has an appropriate diffusibility include, for example, US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent Nos. 96,57.
No. 0 and West German Patent (publication) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,08,820.
Nos. 0,211 and 4,367,282, and British Patent No. 2,102,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing a development inhibitor is described in Research Disclosure No. 17643 VII
Patents described in section -F, JP-A-57-151944
No., No. 57-154234, No. 60-184248
And those described in U.S. Pat. No. 4,248,962 are preferred. Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No. 2,
Nos. 097, 140 and 2, 131, 188, JP-A-59-157538 and JP-A-59-170840 are preferred.

Other couplers usable in the light-sensitive material of the present invention include, for example, US Pat.
No. 4,427, etc., US Pat.
No. 283,472, Nos. 4,338,393, 4,310,618, etc., and DIRs described in JP-A-60-185950, JP-A-50-24252, and the like. Redox compounds or DIR coupler-releasing couplers, couplers that release dyes that recolor after release as described in EP 173302A, Research Disclosure No. And bleaching accelerator releasing couplers described in JP-A Nos. 11,449, 24241 and JP-A-61-201247, and ligand releasing couplers described in U.S. Pat. Nos. 4,553,477.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are disclosed in U.S. Pat.
No. 2,027. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or more used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, cycyclohexyl phthalate,
2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate) ,
Esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl) Benzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (E.g., bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate) aniline derivatives (e.g., N, N-dibutyl-2-butoxy-5-tert-octyl aniline) ), Hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like.
As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate, dimethylformamide and the like.

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

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

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating and extrusion coating can be used. U.S. Pat. No. 2,
Nos. 681, 294, 2, 761, 791, 3, 526, 528 and 3, 508, 947, etc., may be used to simultaneously apply multiple layers.

The present invention can be applied to various color and black-and-white photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer photosensitive materials and heat developable color photosensitive materials. it can. Research Disclosure, N
o. U.S. Pat. No. 4,126,461 and British Patent No. 2,102,1 by utilizing a three-color coupler mixture such as described in US Pat.
The present invention can be applied to black-and-white photographic materials for X-rays and the like by utilizing a black color coupler described in JP-A No. 36 and the like. Plate making film such as squirrel film or scanner film, X for direct / indirect medical or industrial use
Line film, negative black and white film for photography, black and white photographic paper, C
The present invention can also be applied to OM or ordinary microfilms, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials.

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, a peeling (peel apartment) type or JP-B-46-16356, JP-B-48-33697,
JP-A-50-13040 and British Patent No. 1,33
No. 0,524, it is possible to increase the rigidity of a film unit of a type not requiring peeling. The use of a polymeric acid layer protected by a neutralization timing layer in any of the above types of formats is advantageous in widening the processing temperature latitude. When used in color diffusion transfer photography, it may be used by adding it to any layer in the light-sensitive material, or may be used as a developing solution component enclosed in a processing solution container.

Various exposure means can be used for the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the irradiation light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury lamps, fluorescent lamps, and strobe or metal-burning flash bulbs are common. A gas, dye solution or semiconductor laser that emits light in the wavelength range from ultraviolet to infrared,
Light emitting diodes and plasma light sources can also be used as recording light sources. Also, a phosphor screen (such as a CRT) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
Exposure means in which a linear or planar light source is combined with a micro-shutter array using D) or lanthanum-doped lead titanium zirconate (PLZT) can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used for developing the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Typical examples thereof include 3-methyl-4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These diamines are generally more stable in a salt than in a free state, and are preferably used.

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

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

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

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specifications: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988; No.53-32736, No.53-57831, No.3
No. 7-418, No. 53-65832, No. 53-726
No. 23, No. 53-95630, No. 53-95731
No. 53-104232, No. 53-124424
No., 53-141623, 53-28426,
Research Disclosure, No. 17129 (1
A compound having a mercapto group or a disulfide group described in, for example, JP-A-50-140129;
-8506, JP-A-52-20832 and 53-3
No. 2,735, U.S. Pat. No. 3,706,561; thiourea derivatives described in West German Patent No. 1,127,715, iodides described in JP-A-58-16235; West German Patent No. 966,410; Polyethylene oxides described in JP-A-2,748,430; Polyamine compounds described in JP-B-45-8836;
No. 4, No. 49-59644, No. 53-94927,
Compounds and iodides described in JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940;
Bromide ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,893,858.
No. 1, West German Patent No. 1,290,812, JP-A-53-9
The compounds described in No. 5630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the sensitizer. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide, and thiosulfates are generally used. As a preservative for the bleach-fixing solution or the fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

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

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

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate and the like as a membrane pH adjuster after the treatment. In addition, in the case of a color sensitizer for photography, a step (washing-stabilization) usually performed after fixing can be replaced with the above-mentioned stabilizing step and washing step (water saving processing). On this occasion,
When the amount of the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed. The water washing and stabilizing treatment time of the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes, depending on the type of photosensitive material and processing conditions.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,592, U.S. Pat. No. 3,342,599, Research Disclosure, 14850 and no. No. 15159, the Schiff base compound; JP-A-56-6235, aldol compounds described in JP-A-13924, metal complex salts described in U.S. Pat. No. 3,719,492, urethane-based compounds described in JP-A-53-135628,
Nos. 56-16133, 56-59232, 56
-67842, 56-83734, 56-83
No. 735, No. 56-83736, No. 56-89735
Nos. 56-81837, 56-54430, 56-106241, 56-107236, and 5
Examples thereof include precursors of various salt types described in JP-A-7-97531 and JP-A-57-83565.
The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones as needed for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339 and JP-A-57-144547.
No. 57-111147, No. 58-50532,
No. 58-50536, No. 58-50533, No. 58
Nos. -50534, 58-50535 and 58-
No. 115438.

The various processing solutions used in the present invention are 10 to 50 ° C.
Used in A temperature of 33 ° C. to 38 ° C. is standard, but higher temperatures can accelerate the processing and shorten the processing time, and lower temperatures can achieve higher image quality and improved processing solution stability. it can. Further, in order to save silver of the photosensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed. Heaters, temperature sensors,
A liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, and the like may be provided. In the case of continuous processing, a certain finish can be obtained by using a replenisher for each processing liquid to prevent fluctuations in the liquid composition. The replenishment amount is
It can be reduced to half or less than the standard replenishing amount for cost reduction and the like. When the light-sensitive material of the present invention is a color paper, it can be subjected to a bleach-fixing process, if necessary, even if it is a color photographic material for photography.

[0073]

The present invention will be described below in more detail with reference to specific examples, but the present invention is not limited thereto. Example 1 "Emulsion A-1: Silver bromide octahedral emulsion" pH 5.0 containing 36 g of gelatin and 0.25 g of potassium bromide kept at 75 ° C.
Silver nitrate aqueous solution (A)
gNO ₃ 0.5 g) and potassium bromide aqueous solution (K
36 ml of (0.38 g of Br) was added over 10 minutes, and then 176 ml of an aqueous solution of silver nitrate and an aqueous solution of potassium bromide of the same concentration were added by the double jet method over 7 minutes. After additional addition of 1.4 g of potassium bromide, 1010 ml of an aqueous silver nitrate solution (140.7 g of AgNO ₃ ) was initially added at a flow rate of 1.8 ml / min at an accelerated rate of 78 minutes, and simultaneously an aqueous solution of potassium bromide (107.1 g) was added. /
l) was added while controlling the silver potential at 0 mV (vs. the saturated calomel electrode). Further, 578 ml of an aqueous solution of silver nitrate (50.1 g of AgNO ₃ ) and 578 ml of an aqueous solution of potassium bromide (35.1 g of KBr) were added at a constant flow rate over 24 minutes. After completion of the addition, the temperature was lowered to 35 ° C., after which soluble salts were removed by a usual precipitation method, the temperature was raised again to 40 ° C., gelatin was added and dissolved, and the pH was adjusted to 6.3. The obtained particles have a projected area diameter of 0.8 μm.
Of monodispersed silver bromide octahedral grains (coefficient of variation: 10%). "Emulsions A-2 to A-5: silver bromide octahedral emulsion doped with hexacyano metal complex" (comparative example) 5 × 10 ^{− in} 578 ml of an aqueous potassium bromide solution used at the end of grain formation of emulsion A-1. ⁴ M following compounds of (1),
Emulsion A obtained in exactly the same manner as Emulsion A-1, except that it contains (2), (3), (4) or (5), respectively.
-2, A-3, A-4, A-5 and A-6 were prepared.

(1) K ₄ [Fe (CN) ₆ ] · 3H ₂ O (2) K ₃ [Fe (CN) ₆ ] (3) K ₄ [Ru (CN) ₆ ] (4) K ₃ [Co (CN) ₆ ] (5) K ₃ [Ir (CN) ₆ ]

"Emulsion B-1: a silver bromide octahedral emulsion washed with a halide salt" The same operation as in the case of emulsion A-1 was performed until the addition of silver nitrate was completed.
A 100% aqueous solution of potassium bromide (100 ml) was added, and the mixture was stirred for 10 minutes to wash. After the temperature was lowered to 35 ° C. and the soluble salts were removed by the ordinary sedimentation method, the temperature was raised again to 40 ° C., gelatin was added and dissolved, and the pH was adjusted to 6.3. The resulting grains were monodisperse silver octahedral grains having a projected area diameter of 0.8 μm (coefficient of variation: 10%).

"Emulsions B-2 to B-5: octahedral silver bromide emulsion doped with hexacyano metal complex" (in the present invention) 5 to 578 ml of an aqueous solution of potassium bromide used at the end of grain formation of emulsion B-1 Emulsion B-1 was obtained in exactly the same manner as in Emulsion B-1, except that each of the compounds (1), (2), (3), (4) and (5) was contained at × 10 ^-4 M (mol / dm ³ ). Emulsions B-2, B-3, B-4, B-5
And B-6 were prepared.

Next, A-2, A-3, A-4, A-5,
A-6, B-2, B-3, B-4, B-5 and B-6
Of emulsion, 1.2 × 10 ⁻⁵ mol / mol silver sodium thiosulfate, 3.6 × 10 ⁻⁶ mol / mol silver potassium chloroaurate, and 5.1 × 10 ⁻⁴ mol / mol silver thiocyanate By adding potassium acid and heating at 60 ° C. for 60 minutes, chemical sensitization was optimally performed.

The emulsions were prepared by adding gelatin and sodium dodecylbenzenesulfonate to form a mixture of gelatin, polymethylmethacrylate particles, 2,4-dichloro-6-
Coated by extrusion with a protective layer containing sodium hydroxy-s-triazine.

The samples were exposed to sensitometric exposures (1 sec and 10 ^-3 sec) via an optical wedge.
After developing with a MAA-1 developer having the following formulation at 20 ° C. for 10 minutes, the solution was stopped, fixed, washed with water and dried by a conventional method, and the optical density was measured. The relative sensitivity was represented by the reciprocal of the exposure required to obtain an optical density of fog + 0.1. Here, the sensitivity was represented by setting the value of sample A-2 to 100.

[0080]

[Table 1]

MAA-1 developer Metol 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g KBr 1.0 g Add water and add 1 liter

As is evident from Table 1, the silver halide emulsion containing the dopant prepared by washing with the halide salt of the present invention has high sensitivity in both low light exposure and high light exposure.

Example 2 “Emulsion C-1: Cubic silver bromide emulsion” pH 5.0 containing 0.25 g of potassium bromide and 40 g of gelatin kept at 75 ° C.
The aqueous silver nitrate solution and the aqueous potassium bromide solution were stirred at 880 ml of an aqueous solution of
Min (equivalent to 0.05 g / min of AgNO ₃ ) for 10 minutes, followed by co-addition at 25.2 ml / min for 7 minutes. During this addition, the pBr was constant. Subsequently, while controlling the silver potential at +100 mV (vs. a saturated calomel electrode), the silver nitrate aqueous solution is accelerated (primary) using a silver nitrate aqueous solution and a potassium bromide aqueous solution 10 times the concentration during nucleation, and Added for 100 minutes. After completion of the addition, the temperature was lowered to 35 ° C., after which soluble salts were removed by a usual precipitation method, the temperature was raised again to 40 ° C., gelatin was added and dissolved, and the pH was adjusted to 6.3. The obtained particles were monodispersed silver bromide cubic particles having a projected area diameter of 0.7 μm (coefficient of variation: 10%).

"Emulsions C-2 to C-5: silver bromide cubic emulsion doped with hexacyano metal complex" (Comparative Example) An aqueous silver nitrate solution of emulsion C-1 was added (primary) 14 minutes before the completion of the addition. 1.9 × 10 ^-4 M (mol / dm ³ )
Emulsion C- obtained exactly in the same manner as Emulsion C-1, except that an aqueous solution containing each of the above compounds (1), (2), (3), (4) and (5) was added by triple jet. 2, C-3, C-4, C-5 and C-6 were prepared.

"Emulsion D-1: Cubic silver bromide emulsion washed with a halide salt" The same procedure as in Emulsion C-1 was performed until the addition of silver nitrate was completed.
A 100% aqueous solution of potassium bromide (100 ml) was added, and the mixture was stirred for 10 minutes to wash. After the temperature was lowered to 35 ° C. and the soluble salts were removed by the ordinary sedimentation method, the temperature was raised again to 40 ° C., gelatin was added and dissolved, and the pH was adjusted to 6.3. The resulting grains were monodisperse silver octahedral grains having a projected area diameter of 0.8 μm (coefficient of variation: 10%).

"Emulsion D-2 to D-5: Cubic silver bromide emulsion doped with hexacyano metal complex" (invention) Accelerated (primary) addition of silver nitrate aqueous solution of emulsion D-1 14 minutes before completion of addition 1.9 × 10 ^-4 M (mol / dm ³ )
The above compounds (1), (2), (3), (4) and (5) are prepared in exactly the same manner as for emulsion D-1 except that an aqueous solution containing each of the following chemical formulas is added by triple jet. The resulting emulsions D-2, D-3, D-4, D-5 and D-6 were prepared.

Next, C-2, C-3, C-4, C-5,
C-6, D-2, D-3, D-4, D-5 and D-6
2.9 × 10 ⁻⁵ mol / mol silver sodium thiosulfate and 5.9 × 10 ⁻⁶ mol / mol silver potassium chloroaurate were added to the emulsion of Example 1 and the mixture was heated at 60 ° C. for 60 minutes to chemically increase the emulsion. The feeling was optimally applied.

These emulsions were added to a triacetyl cellulose film support having an undercoat layer by adding gelatin and sodium dodecylbenzenesulfonate to form gelatin, polymethyl methacrylate particles, 2,4-dichloro-6-
Coated by extrusion with a protective layer containing sodium hydroxy-s-triazine.

The samples were exposed, developed, and measured for optical density in the same manner as in Example 1. Relative sensitivity is fog + 0.
It was expressed as a relative value of the reciprocal of the exposure required to obtain an optical density of 1. Here, the sensitivity was represented by setting the value of sample C-2 to 100.

[0090]

[Table 2]

As is clear from Table 2, the silver halide emulsion containing the dopant produced by washing with the halide salt of the present invention shows that both the low-light exposure and the high-light exposure can be performed on a silver bromide cube. At high sensitivity, indicating that these effects do not depend on the crystal habit.

Example 3 "Samples E-2 to E-5 and F-2 to F-6: color development of octahedral silver bromide emulsion doped with hexacyano metal complex"
A-2, A-3, A-4, A-5 prepared in Example 1
A-6, B-2, B-3, B-4, B-5 and B-6
After optimally sensitizing the emulsion of Example 1 with sodium thiosulfate, potassium chloroaurate and potassium thiocyanate, magenta coupler; 3- {3- [2- (2,4-di-te
rt-amylphenoxy) butyrylamino] benzoylamino} -1- (2,4,6-trichlorophenyl) pyrazolin-5-one

Oil: tricresyl phosphate

Stabilizer: 4-hydroxy-6-methyl-
1,3,3a-7-tetrazaindene

Coating aid: sodium dodecylbenzenesulfonate

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

A preservative: phenoxyethanol was added, and the mixture was extruded onto a triacetyl cellulose film support having an undercoat layer together with a gelatin protective layer containing fine particles of polymethyl methacrylate.
2, E-3, E-4, E-5, E-6, F-2, F-
3, F-4, F-5 and F-6 were obtained, respectively. The samples were exposed to sensitometric exposures (1 sec and 10 ^-3
Sec), and the following color development processing was performed. The concentration of the treated sample was measured with a green filter. The relative sensitivity was represented by the reciprocal of the exposure required to obtain an optical density of fog + 0.1. Here, the sensitivity was represented by setting the value of sample E-2 to 100.

[0098]

[Table 3]

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

Color developer sodium nitrilotriacetate 1.0 g sodium sulfite 4.0 g sodium carbonate 30.0 g potassium bromide 1.4 g hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-βhydroxyethylamino) 2-Methyl-aniline sulfate 4.5 g 1 liter by adding water

Bleaching solution Ammonium bromide 160.0 g Aqueous ammonia (28%) 25.0 ml Ethylenediamine-tetraacetate sodium salt 130 g Glacial acetic acid 14 ml Add water to 1 liter

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

Stabilizing solution Formalin 8.0 ml Add water and add 1 liter

As shown in Table 3, the emulsion washed with the halide salt exhibited high sensitivity under both low illuminance and high illuminance exposure.

[0105]

As is clear from the examples, by applying the present invention, it is possible to provide a silver halide photosensitive material having high sensitivity and little dependence on exposure illuminance.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-183647 (JP, A) JP-A-48-60916 (JP, A) JP-A-54-7321 (JP, A) JP-A-4- 287036 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 1/015 G03C 1/07-1/09

Claims (2)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains a hexacyano metal complex salt and is gold-sensitized. And 10 before applying the gold sensitization.
^A silver halide photographic material comprising an emulsion washed with an aqueous solution of a halide salt having a concentration of ^-4 M or more. 2. The method according to claim 1, wherein said halide salt aqueous solution comprises
It is characterized by being the same halide salt aqueous solution as the composition
The silver halide photographic light-sensitive material according to claim 1.