JPH11202440A - Photographic silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photographic silver halide emulsion high in sensitivity. SOLUTION: This photographic silver halide emulsion contains an iridium complex in silver halide grains in a localized layer higher by >=10 times in its concentration than the other parts of each grain and its localized layer is situated in the surface layer of each grain occupying <=12 volume % of its grain. This iridium complex is represented by the formula: [IrXp (H2 O)m ]n , in which X is a halogen atom; (p) is 3, 4, or 5; m=6-p, n=2-, 1- or 0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material. More specifically, the present invention relates to a highly sensitive silver halide photographic material.

[0002]

2. Description of the Related Art In silver halide photographic light-sensitive materials, sensitivity,
Fine granularity and low fog are required as basic performance. As a means for satisfying this, there is a metal doping technique. This metal doping technology aims to improve the physical properties of silver halide grains and increase the efficiency (quantum sensitivity) of converting photoelectrons into a development-active latent image. Is incorporated (doped) in silver halide grains and in the grain surface phase. As a result, the characteristics of the silver halide grains are modified so that the emulsion can be designed to have a desired basic performance such as high sensitivity or desensitized high contrast.

A silver halide emulsion prepared by adding a metal compound during or after the formation of silver halide grains is described in Research Disclosur.
e), Vol. 176, No. 17643, Item IA (1978) and Volume 367, Item 36736 (1994). An early representative example of a metal compound doped emulsion was a metal complex of platinum, palladium, iridium, rhodium and ruthenium as shown in U.S. Pat. No. 2,448,060. Disclosed that these metal complexes are water-soluble and have an effect as an antifoggant and a stabilizer by adding a metal complex, and also sensitize especially when a hexacoordinate metal complex of palladium (IV) is added. doing. U.S. Pat. No. 3,690,888 discloses a method for producing silver halide containing a polyvalent metal ion, which comprises the step of producing silver halide grains in the presence of a peptizer mainly composed of an acrylic polymer. It has been disclosed. Bismuth, iridium, lead or osmium ions are mentioned as polyvalent metal ions. The iridium ion in these patents was iridium hexachloride.

JP-A-2-20853 and JP-A-2-2085
No. 4 describes a silver halide emulsion formed in the presence of a rhenium, ruthenium, osmium or iridium complex having at least four or more cyano ligands. The effect is particularly excellent in sensitivity and gradation stability with time, and low illuminance failure is improved. In these disclosures, a new concept is proposed in which the hexacoordinated metal complex is doped by displacing seven vacancies of one silver ion and six adjacent halide ions inside the crystal. This differs from the conventional view of metal doping, in which only metal ions replace silver ions.

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 for preparing a photographic silver halide emulsion comprising stopping the addition of iridium ion long before stopping the addition of silver salt such that substantially no iridium ion remains. The iridium ion described in this disclosure was an iridium hexachloride complex.

Further, iridium complexes are disclosed in Japanese Unexamined Patent Publication No.
By adding a Group VIII metal complex to Emulsion No. 1244, an emulsion having high sensitivity is obtained. This metal complex includes an iridium complex, but iridium was a polynuclear complex having two or more nuclei.

With respect to iridium complexes containing water ligands,
As a state where the photoelectrons doped into silver bromide are captured,
[(IrCl ₅ H ₂ O)) ^3- . 2V] and [(IrCl
₄ (H ₂ O) ₂ ) ^2- . 3V] measured by ESR
The photoelectron lifetime at 00K is "Crystal Lattice Defect and Amorphous Material (Cryst.
Latt. Def. And Amorph. Mat.), Vol. 18, 297
(1989). According to the report, it is reported that the photoelectron lifetime becomes longer as the number of water ligands increases. Although there is no specific description of the doping method in this document, silver halide grains are uniformly doped.

As described above, in a silver halide photographic light-sensitive material, a photographically useful effect can be expected by doping a silver halide grain with a metal dopant.

[0009]

An object of the present invention is to provide a silver halide photographic emulsion having a high sensitivity.

[0010]

The above object has been attained by the following. That is, a localized phase containing an iridium complex represented by the following general formula (I) in silver halide grains and having a concentration of the iridium complex 10 times or more higher than that of the other portion is reduced to 12% or less of the grain volume. This was achieved by a silver halide photographic emulsion characterized by having a surface phase. Formula (I) [IrX _p (H ₂ O) _m ] ⁿ wherein X represents a halogen, and p = 4, 5, or 6,
m = 6-p, n = 2-, 1- or 0.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Methods for synthesizing and identifying the compounds of the present invention are described in “Inorganic Chemistry”, Vol.
9 (1965) and "Journal of Chemical
Physics, "Vol. 22, 2064 (1
954). Specific examples of the iridium complex of the present invention are shown below, but the compounds of the present invention are not limited thereto. (I-1) [IrCl ₅ (H ₂ O)] ^{2- (I-2)} [IrCl ₅ (H ₂ O)] ^- (I-3) [IrCl ₄ (H ₂ O) _2] ^- (I- 4) [IrCl ₄ (H ₂ O) ₂ ] (I-5) [ItCl ₃ (H ₂ O) ₃ ] (I-6) [IrBr ₅ (H ₂ O)] ^2- (I-7) [IrBr ₅ (H ₂ O)] ^- (I-8) [IrBr ₄ (H ₂ O) _2] ^- (I-9) [IrBr ₄ (H ₂ O) _2] (I-10) [ItBr ₃ (H ₂ O) ₃ ]

(I-11) [IrI ₅ (H ₂ O)] ^2- (I-12) [IrI ₅ (H ₂ O)] ⁻ (I-13) [IrI ₄ (H ₂ O) ₂ ] ⁻ (I-14) [IrI ₄ (H ₂ O) ₂ ] (I-15) [ItI ₃ (H ₂ O) ₃ ]

Since the iridium complex of the present invention exists in an ionic form in an aqueous solution, the counter cation is not important. Among them, sodium ions, potassium ions, which are easily miscible with water and are suitable for the precipitation operation of silver halide emulsions,
It is preferable to use alkali metal ions such as rubidium ion, cesium ion and lithium ion, ammonium ions, and alkylammonium ions represented by the following general formula (II). Formula (II) [R ₁ R ₂ R ₃ R ₄ N] ^{+ wherein} R ₁ , R ₂ , R ₃ and R ₄ are a methyl group, an ethyl group, a propyl group, an iso-propyl group, an n-butyl Represents a substituent arbitrarily selected from an alkyl group such as a group. Among _{them, R 1, R 2, R} 3 and R ₄ are all equal substituent tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion and tetra (n- butyl) ammonium ion.

The iridium complex of the present invention may be mixed with a water-miscible organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.) in addition to water. It can be dissolved and added.

The iridium complex of the present invention is added directly to a reaction solution at the time of forming silver halide grains, or is added to an aqueous halide solution for forming silver halide grains or to a solution other than the above. It is preferable to include them by carrying out. Further, a method of adding the compound of the present invention in the form of doped fine particles may be used. Further, the above addition methods may be used in combination.

The addition amount of the iridium complex of the present invention is such that the local concentration of the silver halide-doped phase is 1 × 1 per mole of silver.
It is preferably from 0 ^-4 mol to 2 × 10 ^-2 mol, and more preferably from 5 × 10 ^-4 mol to 1 × 10 ^-2 mol.

The doping position of the iridium complex of the present invention is as follows:
It is preferable to have a localized phase having a concentration of the iridium complex at least 10 times higher than that of the other portion in a surface phase of 12% or less of the particle volume, and more preferably 3% or less. Further, the epitaxial phase formed on the particle surface may be doped.

The concentration other than that of the localized phase is one-tenth or less of the doping concentration of the localized phase. Preferably, it is 1/100 or less, and the addition amount is 10 ^-6 or less per mol of silver. Preferably, the compound of the present invention is not added except for the localized phase. The addition amount of the whole grains is 1.2 × 10 ⁻³ mol or less per mol of silver. Preferably 2 ×
10 ^-4 mol or less.

In the case of an epitaxial phase formed on the surface of a particle, the content of the epitaxial phase is preferably 12% or less, more preferably 3% or less, based on the particle volume. In this case, the compound of the present invention may be uniformly doped in the entire epitaxial phase, or may be doped in the inside or a part of the surface of the epitaxial phase. Further, both the surface phase and the epitaxial phase of the particles of the substrate may be doped with the compound of the present invention. Also in this case, the doping phase of both the surface phase and the epitaxial phase of the particles of the substrate is 12% of the total volume of the particles.
It is as follows. Preferably, it is 3% or less.

The volume of the localized phase with respect to the whole particles is 1 to 15% by weight of the whole particles. Preferably it is 1 to 5% by weight.

The method for measuring the doping amount and the doping ratio in the silver halide grains of the iridium complex of the present invention includes the atomic absorption method for the central metal of the metal complex,
ICP (Inductively Coupled Plasma Spectrometr)
y; inductively coupled high frequency plasma spectroscopy) and ICP
MS method (Inductively Coupled Plasma Mass Spectromet
ry; inductively coupled plasma mass spectrometry) or the like.

In the present invention, the halogen composition may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochloride and silver chloroiodobromide. On the other hand, to increase the high illumination sensitivity,
For the purpose of increasing the spectral sensitization sensitivity or increasing the stability over time of a light-sensitive material, a emulsion containing 0.01 to 3 mol% of silver iodide on the emulsion surface as described in JP-A-3-84545. In some cases, silver chloride grains are preferably used. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform.

The average size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 0.1 to 2 μm is preferred. The particle size distribution is preferably a monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of the silver halide grains contained in the photographic emulsion is
Regular (regu) like cube, tetrahedron or octahedron
One having an lar) crystal form, one having an irregular (for example, spherical, plate-like) crystal form, or one having a complex form thereof can be used. For tabular grains, silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chlorobromoiodide tabular grains having a principal plane of {100}, or silver chloride having a principal plane of {111}; Any tabular plate of silver chlorobromide, silver bromide, silver iodobromide and silver chlorobromoiodide may be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, 50% or more, preferably 70% or more of the particles having the regular crystal form,
More preferably, the content is 90% or more. In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

For the purpose of preparing monodispersed silver halide grains, a silver halide solvent can be used. Preferred silver halide solvents include thiocyanates, thioethers, thioureas, and the like, and ammonia can also be used in combination as long as it has no adverse effect. For example, thiocyanates (US Pat. No. 2,222,2)
No. 64, No. 2,448,534, No. 3,320,
No. 069), thioether compounds (US Pat.
No. 71,157, No. 3,574,628, No. 3,
No. 704, 130, No. 4, 297, 439, No. 4,
276,347) and thione compounds (JP-A-53-1)
Nos. 44319, 53-82408, 55-777
No. 37 etc.), amine compounds (JP-A-54-100717)
No. etc.) can be used.

Also, US Pat. No. 5,147,771;
Monodispersing agents based on polyalkylene oxide block copolymers described in US Pat. Nos. 5,147,772, 5,147,773 and JP-A-8-320529 can also be used.

For the production of the silver halide emulsion used in the present invention, any known method can be used. 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. A concrete method is described in P. Glafkides, "Chimie et Physique Photographequ."
e) "(Paul Montel, 1967)
GFDuffin, Photographic Emulsion Chemistry (Photog)
raphic Emulsion Chemistry) (Focal Press, 1966), VLZeli
kman), “Making and Coating Photographic Emulsion (Making and Coating)
Photographic Emulsion) "(Focal Press, 1
964). That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt with a soluble halide is a one-side mixing method, a simultaneous mixing method,
Any of these combinations and the like may be used. As one type of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is formed,
The double jet method can also be used. Also, British Patent No. 1,535,016, JP-B-48-36890.
No., No. 52-16364, etc.,
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.
It is preferable to use a method of changing the concentration of the aqueous solution as described in JP-A-2,445, JP-A-55-158124, or the like, to allow rapid growth within a range not exceeding the critical supersaturation. These methods are preferably used because silver halide grains grow uniformly without causing renucleation.

In the course of silver halide grain formation or physical ripening, a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iron salt and the like may be coexisted.

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
99, 290A2, 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, even for grains having a bonding structure, the silver iodide content of the host crystal is high, and the silver iodide content of the bonding crystal is relatively low,
The opposite particles may be used. 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 used in the present invention may be prepared by subjecting the grains to a rounding treatment as disclosed in European Patent Nos. 96,727B1 and 64,412B1, or by DE-2,306,447C2, and JP-A-60 / 60. −
The surface may be modified as disclosed in 221320. The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

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.

As a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sodium alginate;
Various sugar derivatives such as starch derivatives; mono- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Synthetic hydrophilic polymeric substances can be used. As the gelatin, besides lime-processed gelatin for general use, acid-processed gelatin and the journal of the Japan Society of Science Photography (Bull. Soc. Phot. Japan), 16
Enzyme-treated gelatin as described in Vol. 30, No. 30 (1966), or a hydrolyzate of gelatin can be used. Gelatin obtained by oxidizing the methionine portion of gelatin with hydrogen peroxide can also be preferably used.

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. Specific examples thereof include chromium salts, aldehyde salts (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol-based compounds (dimethylol urea, etc.). 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 polymer having a vinylsulfone group in the side chain, etc.) are preferable because they can rapidly 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-pyridinimethylene) pyrrolidinium-2-naphthalenesulfate) are also fast and excellent in curing speed.

In the present invention, sulfur sensitization, selenium sensitization,
Tellurium sensitization, noble metal sensitization and reduction sensitization can be used alone or in combination.

In the sulfur sensitization, there is a sulfur sensitization method using a so-called unstable sulfur compound capable of forming silver sulfide by reacting with silver ions. Specifically, P. Glafkides, "Chimi
et Physique Photographeque ”(Paul Montel, 1
987, 5th edition), Research Ticlosure, 3
07105, edited by THJames, "The Theory of the P
hotographic Process ”(published by Macmillan, 1977,
4th edition), H. Frieser, "Die Grundlagender Photogr
aphischen Prozess mit Silver-halogeniden "(Akadem
ische Verlagsgeselbshaft, 1968). Specific examples of the sulfur sensitizer include thiosulfates (eg, sodium thiosulfate, p-toluenethiosulfonate, etc.), thioureas (eg, allylthiourea, N, N′-diphenylthiourea, triethylthio). Urea, acetylthiourea, N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, etc.), thioamides (eg, thioacetamide, N-phenylthioacetamide, etc.), rhodanines (eg, rhodanine, N -Ethyl rhodanine, 5-benzylidene rhodanine, 5-benzylidene-N-ethyl-rhodanine, diethyl rhodanine, etc.) and thiohydantoins, 4-oxo-oxazolidin-2-thiones , Dipolysulfides, thiosulfonic acids, mercapto compounds such as cysteine, polythiophene Salt, elemental sulfur, can be used such as sodium sulfide.

In the selenium sensitization, known unstable selenium compounds, specifically, colloidal metal selenium, JP-B-44-15748 and JP-B-43-1348 are used.
9, JP-A-4-25832, JP-A-4-109240
No. 4,147,250, 4-271341, 4-40324, and the like. More specifically, selenoureas (for example, aliphatic selenoureas such as selenourea, N, N-dimethylselenourea, N, N-diethylselenourea, and 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.

Regarding tellurium sensitizers, see 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 800,958, Journal of Chemical Society Chemicals, Inc.
Communication (J. Chem. Soc., Chem. Commun.), 6
35 (1980), 1102 (1979), 645
(1979), Journal of Chemical Society Parkinson Transaction (J. Chem. So
c., Perkin. Trans.) 1, 2191 (1980), JP-A Nos. 4-204640 and 4-333430, and the like. More specifically, colloidal tellurium, telluroureas (for example, allyl tellurourea, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N ′, N′-dimethyltellurourea, N, N ′ -Dimethylethylene tellurourea,
N, N′-diphenylethylene tellurourea), isotellurocyanates (eg, allyl isotellurocyanate), telluroketones (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 aforementioned P. Grafkide
Chimie et Physique Photographique, by Paul M.
No. sensitizers such as gold, platinum, palladium, and iridium described in Research Telclosure, No. 307105, etc., published by Ontel, 1987, 5th edition) can be used in combination. In this case, it is particularly preferable to use a gold sensitizer in combination. Specifically, in addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide, US Pat. No. 2,642,36
No. 1, 5,049,484 and 5,049,4
No. 85 or the like can be used.

In reduction sensitization, the aforementioned P. Grafkides
Author, Chimie et Physique Photographique (Paul Mo
ntel, 1987, 5th edition), Research Ticlosure, 307, 307105, and the like, and known reducing compounds 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), chloride 1
Tin, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas, and the like can be used.

These chemical sensitizations may be used alone or in combination of two or more.
May be combined, especially when combined with chalcogen sensitization
A combination of gold sensitizations is preferred. Reduction sensitization is halogenated
It is preferably applied at the time of forming silver particles. Used in the present invention
The amount of chalcogen sensitizer used depends on the silver halide used.
Depending on the grains, chemical sensitization conditions, etc., silver halide
10 per mole^-8-10^-2Mole, preferably 10^-7~
5 × 10^-3Use about moles. Precious gold used in the present invention
The use amount of the genus sensitizer is 10 per mole of silver halide. ^-7
-10^-2Use about moles. Chemical sensitization in the present invention
The conditions are not particularly limited, but the pAg is 6 to
11, preferably 7 to 10, and a pH of 4-1.
0, the temperature is 40 to 95 ° C, preferably 45 to 85
° C.

The silver halide photographic emulsion used in the present technology is disclosed in Japanese Patent Application Laid-Open No. A mercaptoheterocyclic compound and a tetraazaine compound described in JP-A-225445 can be contained. In addition, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles , Aminotriazoles, benzotriazoles, nitrobenzotriazoles, azaindenes such as triazaindenes, pentaazaindenes and the like; antifoggants such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide and the like Alternatively, many compounds known as stabilizers can be added.

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

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

The silver halide photographic emulsion used in the present technology may contain 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. Azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinthione; azaindenes Many compounds known as antifoggants or stabilizers, such as, for example, triazaindenes, pentaazaindenes and the like; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc. can be added.

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, accelerating development, increasing contrast, sensitizing).

The silver halide grains of the present invention may be further doped with a metal complex of iron, ruthenium, osmium, cobalt, rhodium or iridium (described later) in order to achieve the desired photographic performance. Can be. One of these iron, ruthenium, osmium, cobalt, rhodium or iridium (described later) complexes may be used alone, or two or more of the same metal and different metal complexes may be used in combination. The amount of addition varies greatly depending on the type of the metal complex used, but is 10 ^-9 to 1 per mol of silver halide.
0 ^-2 mol is preferable, and 10 ^-8 per mol of silver halide is used.
Most preferred is from 10 to 10 ^-4 mol. Ruthenium, osmium, cobalt, rhodium or iridium (see below)
May be added at any stage before the preparation of silver halide grains, that is, before and after nucleation, growth, physical ripening, and chemical sensitization. These metal complexes can be added by dissolving them in water or a suitable organic solvent miscible with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). The addition method may be mixed with the halide solution or performed in a single solution,
Alternatively, it may be added in the form of fine silver halide grains doped in advance. Further, these methods may be added in combination several times.

The iridium complex is a trivalent or tetravalent iridium complex other than the general formula (I), for example, hexachloroiridium (III) complex salt, hexachloroiridium (IV) complex salt, hexabromoiridium ( III) complex salts, hexabromoiridium (IV) complex salts, hexaiodoiridium (III) complex salts, hexaiodoiridium (IV) complex salts, hexaammineiridium (III) complex salts, and hexaammineiridium (IV) complex salts. The present invention is not limited to these. Except for the hexacyanoiridium complex represented by the following general formula (III), the addition amount of these iridium complexes is preferably in the range of 10 ^-9 to 10 ^-4 mol per mol of silver halide.
Most preferably, the amount is from 10 ^-8 to 10 ^-5 mol per mol of silver halide.

In addition, by containing a metal complex of iron, ruthenium, osmium, cobalt, rhodium or iridium in the silver halide grains in combination with the compound of the present invention, higher sensitivity can be obtained, and furthermore, the silver halide grains can be produced with higher sensitivity. The hexacyano metal complex represented by the following general formula (III) is preferably used in that the generation of fogging is suppressed even when the photosensitive material is stored for a long period of time.

Formula (III) [M (CN) ₆ ] ^{n- wherein} M represents iron, ruthenium, osmium, cobalt, rhodium or iridium, and n represents 3 or 4. Specific examples of the hexacyano metal complex used in the present invention are shown below.

(III-1) [Fe (CN) ₆ ] ^4- (III-2) [Fe (CN) ₆ ] ^3- (III-3) [Ru (CN) ₆ ] ^4- (III-4) [Os (CN) ₆ ] ^4- (III-5) [Co (CN) ₆ ] ^3- (III-6) [Rh (CN) ₆ ] ^3- (III-7) [Ir (CN) ₆ ] ^{3 -}

The counter cation of these hexacyano metal complexes is also
Alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, and ammonium ions, which are easily miscible with water and are suitable for the precipitation operation of silver halide emulsions, alkyl represented by the above general formula (II) It is preferable to use ammonium ions.

The light-sensitive material of the present invention contains a hydrophilic colloid layer in European Patent No. 3 for the purpose of preventing irradiation and halation and improving safelight safety and the like.
Dyes that can be decolorized by the treatment described in No. 37,490A2, pages 27 to 76 (oxonol dyes, cyanine dyes)
Is preferably added. In addition, Japanese Patent Application Laid-Open No. 2-2822
No. 44, pp. 3-8 and JP-A-3-793.
Dyes such as the dyes described in No. 1, pages 3 to 11, which are contained in a hydrophilic colloid layer in the form of solid particle dispersion and decolorized by development, are also preferably used. In addition, hemioxonol dyes, styryl dyes, merocyanine dyes,
Anthraquinone dyes, azo 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. When these dyes are used, it is preferable to select and use a dye having an absorption such that the spectral sensitivity of the longest wave photosensitive layer is maximally overlapped. Using these dyes, 680
It is preferable that the optical density (the logarithm of the reciprocal of transmitted light or the reflection density in the case of a reflective support) at 0.5 nm or the laser wavelength used for exposure is 0.5 or more in order to improve sharpness.

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 the above-mentioned Research Disclosure No. 176, 17643 (197).
8) in the patents described in VII-CG. As a yellow coupler, for example, U.S. Pat.
No. 933,501, No. 4,022,620, No. 4,326,024, No. 4,401,752, JP-B-58-10739, British Patent 1,425,02.
Nos. 0 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.
Nos. 61,432 and 3,725,067, Research Disclosure, No. 24220 (1984), JP-A-60-33552, Research Disclosure, 24,230 (1984), JP-A-60-436.
No. 59, U.S. Pat. Nos. 4,500,630 and 4,54.
No. 0,654 is preferred. Examples of the cyan coupler include phenol-based and naphthol-based couplers. For example, U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233,
Nos. 4,296,200 and 2,369,929
No. 2,801,171, No. 2,772,16
No. 2, No. 2,895,826, No. 3,772,0
No. 02, No. 3,758,309, No. 4,334,
011 and 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A.
Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,451,559, No. 4,4
27,767 and EP 161 626A are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in, for example, VII- of Research Disclosure, 176, 17643 (1978).
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,926 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred.

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

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

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. A DIR coupler releasing a development inhibitor is disclosed in Research Disclosure, 176, 17643 (1978), section VII-F;
Nos. 7-151944, 57-154234, 60
Preferred are those described in U.S. Pat. No. 4,248,962. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent Nos. 2,097,140 and 2,131,1.
No. 88, JP-A Nos. 59-157638 and 59-170
No. 840 is preferred.

Other couplers usable in the light-sensitive material of the present invention include, for example, US Pat.
No. 4,427, and the like, U.S. Pat.
No. 283,472, No. 4,338,393, No. 4,310,618, etc., and multi-equivalent couplers described in JP-A-60-185950, JP-A-50-24252, etc. Redox compounds or DIR coupler-releasing couplers, couplers that release dyes that recolor after release as described in EP 173,302A;
Disclosure, No. 11449, No. 24241,
Bleaching accelerator releasing couplers described in JP-A-61-201, 247 and the like, ligand releasing couplers described in U.S. Pat. No. 4,553,477 and the like can be mentioned.

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 described in US Pat.
No. 027, etc. 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, di-2-
Ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate,
Bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tri-2-ethylhexyl phosphate) Dodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di-2
-Ethylhexyl phenyl phosphate), benzoates (eg, 2-ethylhexyl benzoate,
Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), alcohols or phenols (eg, iso- Stearyl alcohol,
2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl)
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate) aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octyl aniline), hydrocarbons (eg, paraffin , Dodecylbenzene, diisopropylnaphthalene) and the like. The auxiliary solvent has a boiling point of about 30 ° C. or higher, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C. or lower can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

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

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound described in EP 277,589 A2 together with a coupler. In particular, a combination with a pyrazoloazole coupler or a pyrrolotriazole coupler is preferable. That is, a compound that is chemically bonded to an aromatic amine-based developing agent remaining after the color developing process to form a chemically inert and substantially colorless compound and / or an aromatic amine-based compound remaining after the color developing process It is possible to simultaneously or solely use a compound which chemically reacts with the oxidized form of the color developing agent to form a chemically inert and substantially colorless compound, for example, a color developing agent remaining in a film upon storage after processing. Further, it is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the oxidized product and the coupler.

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Is preferably added.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers may be formed 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. 681,294, No. 2,761,791, No. 3,526,528, and No. 3,508,947.

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, 17
U.S. Pat. No. 4,126,4, by utilizing a three-color coupler mixture as described in US Pat.
The present invention can be applied to black-and-white photosensitive materials for X-rays and the like by utilizing black color couplers described in JP-A-61-61 and British Patent No. 2,102,136. Plate making film such as squirrel film or scanner film, direct / indirect medical or industrial X-ray film,
The present invention can also be applied to negative black-and-white films for photography, black-and-white photographic paper, COM or ordinary microfilms, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials.

When the 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 1,33
No. 5,524, the rigidity of a film unit that does not need to be peeled can be obtained. The use of a polymeric acid layer protected by a neutralization timing layer in any of the above formats is advantageous for widening the processing temperature tolerance. When used in color diffusion transfer photography, it may be used by adding it to any layer in the light-sensitive material, or may be used as a developing solution component enclosed in a processing solution container.

Various exposure means can be used for the light-sensitive material 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 in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. 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 comprises a pH buffer such as an alkali metal carbonate, borate or phosphate, bromide,
It generally contains a development inhibitor or an antifoggant such as iodide, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, preservatives such as hydroxylamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dyes Forming couplers, competing couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity enhancers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonates Chelating agents such as carboxylic acids, West German Patent Application (OLS) No. 2,622,950
The antioxidants described in (1) 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 (II), cobalt (III), chromium (IV), and copper (II), peracids, quinones, and nitrone compounds are used. Representative bleaches include ferricyanide; dichromate; organic complexes of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanol. Complex salts of aminopolycarboxylic acids such as tetraacetic acid or organic acids such as citric acid, tartaric acid and malic acid; 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 ethylene (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 bleaching accelerators are described in the following specifications: U.S. Pat. No. 3,893,858, West German Patents 1,290,812 and 2,059,988, No. 53-32736, No. 53-57831, No. 3
No. 7-418, No. 53-65832, No. 53-726
No. 23, No. 53-95630, No. 53-95731
No. 53-104232, No. 53-124424
No., 53-141623, 53-28426,
Research Disclosure, 17129 (197
Compounds having a mercapto group or a disulfide group described in 8); thiazolidine derivatives as described in JP-A-50-140129; Japanese Patent Publication No. 45-8506
JP-A-52-20832 and JP-A-53-32735.
Thiourea derivatives described in U.S. Patent No. 3,706,561; West German Patent No. 1,127,715;
Iodide described in JP-A-16235; West German Patent No. 966
Polyethylene oxides described in Nos. 410 and 2,748,430; Polyamine compounds described in JP-B-45-8836; and JP-A-49-42434, JP-A-49-59644, and JP-A-53-94927. 54-
Nos. 35727, 55-26506 and 58-1
No. 63940 and iodide and bromide ions can also be used. Of these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly the compounds described in US Pat. Compounds are preferred. Further, U.S. Pat.
The compounds described in 2,834 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, metal salts such as magnesium salts, aluminum salts and bismuth salts, or surfactants to prevent drying load and unevenness, and various Hardening agents and the like can be added as needed. Or waist (LEWe
st), Photographic Science and Engineering (Phot.Sci.Eng.), Volume 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 subjected to countercurrent water washing,
It is common to save water. Further, instead of the water washing step, a multi-stage countercurrent stabilizing step as described in JP-A-57-8543 may be carried out. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds other than the above-mentioned additives are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting the membrane pH (for example, pH 3 to 9), Aldehydes such as monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin can be mentioned as typical examples. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), insecticides (benzoisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol,
Various additives such as a sulfanilamide and a benzotriazole), a surfactant, an optical brightener, and a hardener may be used, and two or more kinds of the same or different target compounds may be used in combination.

It is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate and the like as a membrane pH adjuster after the treatment. In addition, in the case of a color sensitizer for photography, a step (washing-stabilization) usually performed after fixing can be replaced with the above-mentioned stabilizing step and washing step (water saving processing). On this occasion,
When the amount of the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed. The 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.

In the silver halide color light-sensitive material of the present invention, a color developing agent may be incorporated 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-based compounds described in U.S. Pat. Nos. 3,342,592, 3,342,599, and Schiff base-type compounds described in Research Disclosure, 14850 and 15159; No. 13924, the metal complex salt described in U.S. Pat. No. 3,719,492, and the urethane compound described in JP-A-53-135628, as well as JP-A-56-6235 and JP-A-56-135.
No. 16133, No. 56-59232, No. 56-678
No. 42, No. 56-87334, No. 56-83735
Nos. 56-83736, 56-89735, 56-81837, 56-54430, 56-
No. 106241, No. 56-107236, No. 57-9
And various salt-type precursors described in JP-A-7531 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, JP-A-57-144547 and JP-A-5-14447.
Nos. 7-111147, 58-50532, 58-
No. 50536, No. 58-50533, No. 58-505
Nos. 34, 58-50535 and 58-1154
No. 38, etc.

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 in 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 bleach-fixed very generally, and when it is a color photographic material for photography, if necessary.

[0078]

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: silver bromide octahedral seed emulsion pH containing 813.0 g of gelatin and 5.6 g of potassium bromide kept at 75 ° C.
To 20900 ml of 5.0 aqueous solution, 0.2
813.6 ml of a 4 M silver nitrate aqueous solution and 813.6 ml of a 0.26 M potassium bromide aqueous solution were added in 10 minutes, and then a silver nitrate aqueous solution and a potassium bromide aqueous solution of the same concentration were each used for 7.5 minutes and 4027.3 ml by a double jet method. Was added. 316 m of aqueous solution containing 31.6 g of potassium bromide
After adding 1 liter, a 0.90 M silver nitrate aqueous solution 20289 m
1 at a flow rate of 40 ml / min
For 1 minute, and at the same time, a 1.37 M aqueous solution of potassium bromide was added by a double jet while controlling the silver potential at 0 mV (vs. a saturated calomel electrode).
After completion of the addition, the temperature was lowered to 35 ° C., and soluble salts were removed by a usual precipitation method.
0 g was added and dissolved to adjust the pH to 6.5. The obtained particles were monodisperse octahedral particles having a sphere equivalent diameter of 0.55 μm (coefficient of variation: 20%).

"Emulsion B-1: octahedral silver bromide emulsion" (Comparative Example) 515 g of emulsion A (Ag: 0.767 mol) was dissolved in 506.5 ml of an aqueous solution containing 0.65 g of potassium bromide. 40 ml of a 0.41 M silver nitrate aqueous solution and a 0.48 M potassium bromide aqueous solution (solution b-2) were added by double jet control for 2 minutes so as to keep the silver potential at 0 mV (vs. a saturated calomel electrode). 35 ° C after completion of addition
After removing the soluble salts by the usual precipitation method,
The temperature was raised again to 40 ° C., and 28 g of gelatin was added and dissolved.
The pH was adjusted to 6.5. The obtained particles were monodisperse octahedral particles having an equivalent sphere diameter of 0.56 μm (coefficient of variation 23
%)Met.

[0081] To a solution b-2 of the "Emulsion B-2~4 K ₃ IrCl ₆ doped with silver octahedral emulsion bromide" (Comparative Example) Emulsion B, local concentration per mol of silver, respectively 3 × 10 ^- Emulsions B-2, B-3 and B obtained in exactly the same manner as Emulsion B except that K ₃ IrCl ₆ was added so as to be ³ , 6 × 10 ⁻³ and 1.2 × 10 ⁻² mol.
-4 were each prepared.

"Emulsions B-5 to 7: K ₂ IrCl ₅ (H
₂ O) (I-1) silver bromide octahedral emulsion doped with "(present invention) To a solution b-2 of Emulsion B, the local concentration of silver, respectively per mole of ^{3 × 10 -3, 6 × 10} -3 And emulsions B-5 and B- obtained in exactly the same manner as emulsion B except that K ₂ IrCl ₅ (OH ₂ ) was added so as to be 1.2 × 10 ^-2 mol.
6 and B-7 were prepared respectively.

"Emulsions B-8 to 10: K ₂ IrCl ₄ (H ₂
O) ₂ (I-3) silver bromide octahedral emulsion "doped (the invention) To a solution b-2 of Emulsion B, the local concentration of silver, respectively per mole of ^{3 × 10 -3, 6 × 10} -3 And emulsions B-8 and B- obtained in exactly the same manner as emulsion B except that K ₂ IrCl ₄ (OH ₂ ) ₂ was added so as to be 1.2 × 10 ^-2 mol.
9 and B-10 were prepared respectively.

Emulsions B-1 to 10 were prepared by mixing 1.7 × 10 ^-5 mol of sodium thiosulfate per mol of silver, 8.2 × 1
0 ^-6 mol of chloroauric acid were optimally chemically sensitized by the addition to 60 ° C., respectively.

After the emulsions B-1 to B-10 were subjected to the above chemical sensitization, a spectral sensitizing dye of the following compound a was added at 2.9 × 10 ^-4 mol per mol of silver, and the emulsion was heated at 40 ° C. The mixture was heated and stirred for 20 minutes to be adsorbed on the silver halide grains.

[0086]

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Thereafter, gelatin and sodium dodecylbenzenesulfonate were added to each, and gelatin, polymethyl methacrylate particles, 2,4-dichloro-6-hydroxy-s were added onto a triacetyl cellulose film support having an undercoat layer. - respectively extrusion method together with the protective layer containing a triazine sodium salt was applied a silver amount 2 g / m ^2, to obtain a coated samples 1 to 10, respectively.

These samples were exposed to sensitometry exposure (1 second) with an optical wedge filtered with an SC-50 filter, and then developed at 20 ° C. for 10 minutes with a MAA-1 developer having the following formulation. Stop, fix, wash with water, dry according to the law,
The optical density was measured. The fog was determined at the minimum optical density of the sample. The sensitivity was represented by the reciprocal of the exposure required to obtain an optical density of fog + 0.1, and was represented as a relative value with the value of Sample 1 being 100.

MAA-1 developer Metol 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g KBr 1.00 g Add water and add 1 liter

[0090]

[Table 1]

As is clear from Table 1, the compounds K ₂ IrCl ₅ (H ₂ O) (I-1) and K ₂ IrCl ₄ of the present invention were obtained.
It can be seen that the emulsion doped with (H ₂ O) ₂ (I-3) has high sensitivity.

Example 2 "Emulsion C-1: Silver octahedral emulsion" (Comparative Example) 515 g of emulsion A (Ag: 0.767 mol) was dissolved in 506.5 ml of an aqueous solution containing 0.65 g of potassium bromide. Then, 40 ml of a 0.41 M aqueous solution of silver nitrate (solution c-1) and a 0.48 M aqueous solution of potassium bromide (solution c-2) were controlled by a double jet for 8 minutes while keeping the silver potential at 0 mV (vs. a saturated calomel electrode). Was added. After completion of the addition, the temperature was lowered to 35 ° C., the soluble salts were removed by a usual precipitation method, the temperature was raised again to 40 ° C., 28 g of gelatin was added and dissolved, and the pH was adjusted to 6.5. The obtained particles were monodisperse octahedral particles having a sphere equivalent diameter of 0.58 μm (coefficient of variation: 24%).

"Emulsion C-2-4: K ₂ IrCl ₄ (H
_{2 O) 2 (I-3} ) doped with silver bromide octahedral emulsion "(present invention) solution c-1 and respectively the solutions c-2 by the double jet 7 minutes 20 seconds of Emulsion C, 6 minutes, 4 minutes After the addition, K ₂ IrCl ₄ (OH ₂ ) ₂ and the solution c-1 were further added to the solution c-2 by double jet so that the local concentration was 6 × 10 ⁻³ mol per mol of silver. 40 seconds each,
Emulsions C-2, C-3 and C-4 were obtained in the same manner as Emulsion C except that the addition was performed for 2 minutes and 4 minutes, respectively.

"Emulsion C-5: K ₂ IrCl ₄ (H ₂ O)
₂ (I-3) -doped silver bromide octahedral emulsion "(Invention) Emulsion C solution b-2 was mixed with K ₂ IrCl such that the local concentration was 6 × 10 ^-3 mol / mol of silver. ₅ (O
Emulsion C-5 was prepared in exactly the same manner as Emulsion C except that H ₂ ) was added.

These emulsions were chemically sensitized and spectrally sensitized in the same manner as in Example 1, and then coated on a support.
~ 15.

Exposure and development and measurement of the optical density were performed in the same manner as in Example 1. The sensitivity was expressed as a relative value with the sensitivity of Sample 11 being 100.

[0097]

[Table 2]

As is evident from Table 2, the effect of the emulsion doped with the compound (I-3) of the present invention was recognized at 12% or less of the grain surface phase.

Example 3 "Emulsion D-1: Cubic silver chloride emulsion" (Comparative Example) A solution prepared by adding 25 g of deionized gelatin to 845 ml of an aqueous solution containing 4.5 g of sodium chloride, and keeping the solution at 50 ° C. while stirring was added with 0%. .21M silver nitrate aqueous solution (solution a-1)
140ml and 0.21M sodium chloride aqueous solution 140m
1 was quantitatively added for 10 minutes by the double jet method. After 10 minutes, 320 ml of 2.2 M aqueous silver nitrate solution (d-3) and 2.
320 ml of a 2M aqueous sodium chloride solution (d-4) was further quantitatively added for 35 minutes by the double jet method. Five minutes after the completion of the addition, the temperature was lowered to 35 ° C, soluble salts were removed by a normal sedimentation method, the temperature was raised again to 40 ° C, gelatin was added and dissolved, and sodium chloride, a gelatin preservative, and nitric acid were added. Zinc was added to adjust the pH to 6.5. The resulting grains were monodispersed silver chloride cubes having a side length of 0.5 μm (coefficient of variation: 15%).

[0100]: with the "Emulsion D-2~4 K ₃ IrCl ₆ doped with silver chloride cubic emulsions with" (Comparative Example) solution d-3 and d-4 Emulsion D-1, local concentration respectively per silver mole 3 × 10 ^-3, added in triple jet so that the aqueous solution (d-5) on the particle surface phase 3% containing K ₃ IrCl ₆ to be 6 × 10 ^-3 and 1.2 × 10 ^-2 mol Emulsions D-2, D-3 and D-4 were obtained in the same manner as Emulsion D-1, except that the above procedure was repeated.

"Emulsion D-5-7: K ₂ IrCl ₅ (H
₂ O) (I-1) doped silver chloride cubic emulsion "(invention) Along with the solutions d-3 and d-4 of the emulsion D-1, the local concentration was 3 × 10 ^-3 and 6 per mol of silver, respectively. × 10 ⁻³ and 1.2 × 10 ⁻² mol of K ₂ IrCl ₅ (H
Emulsions D-5, D-6 and D-7 obtained in the same manner as Emulsion D-1 except that an aqueous solution (d-5) containing ₂ O) was added by triple jet so that the grain surface phase became 3%. Were prepared respectively.

"Emulsions D-8 to 10: K ₂ IrCl ₄ (H ₂
O) ₂ (I-3) -doped silver chloride cubic emulsion ”(invention) Along with the solutions d-3 and d-4 of the emulsion D-1, the local concentration was 3 × 10 ⁻³ and 6 per mol of silver, respectively. × 10 ⁻³ and 1.2 × 10 ⁻² mol of K ₂ IrCl ₅ (H
Emulsions D-8, D-9 and D-10 obtained in the same manner as Emulsion D-1, except that an aqueous solution (d-5) containing ₂ O) was added by triple jet so that the grain surface phase became 3%.
Was prepared respectively.

"Emulsion D-11 to 13: K ₂ IrCl ₄ (H
With _{2 O) 2 (I-3} ) doped with silver chloride cubic emulsions with "(present invention) Emulsion D-1 of the solution d-3 and d-4, the local concentration per mol of silver 6 × 10 ^-3 mol K ₂ IrC
l ₅ (H ₂ O) emulsion except that the aqueous solution (d-5) was added in triple jet so that each becomes 12, 24 or 50% of the grain surface phase is obtained in the same manner as Emulsion D-1 comprising a D -11, D-12 and D-13 were prepared respectively.

These emulsions D-1 to D-13 were combined with 8.0 × 10 ^-5 mole of compound b, 6.7 × 10 ^-3 mole of compound c, and 6.0 × 10 ^-5 mole of thiosulfate per mole of silver. sodium,
1.2 × 10 ⁻⁵ chloroauric acid was added to each and optimally sensitized at 60 ° C. Then, for each,
Sodium dodecylbenzenesulfonate was added, and gelatin, polymethyl methacrylate particles, 2,4 were coated on a triacetyl cellulose film support having an undercoat layer.
2 g of silver by extrusion method together with a protective layer containing sodium dichloro-6-hydroxy-s-triazine
It was coated with / m ^2, to obtain a coated samples 16 and 25, respectively.

[0105]

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[0106]

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After exposing these samples to sensitometry exposure (1 second) through an optical wedge, the MA
After developing with an A-1 * developer at 20 ° C. for 5 minutes, the solution was stopped, fixed, washed with water and dried by a conventional method, and the optical density was measured.
The fog was determined at the minimum optical density of the sample. The sensitivity was represented by the reciprocal of the exposure required to obtain an optical density of fog + 0.1, and was represented as a relative value with the value for sample 16 being 100.

MAA-1 * developer Metol 2.5 g L-ascorbic acid 10.0 g Nabox 35.0 g NaCl 0.58 g Water was added to 1 liter

[0109]

[Table 3]

As is clear from Table 3, the compounds K ₂ IrCl ₅ (H ₂ O) (I-1) and K ₂ IrCl ₄ of the present invention were obtained.
_{(H 2 O) 2 (I} -3) was doped emulsions are high sensitivity,
It can be seen that the effect is obtained when the doped phase is 12% or less.

Example 4 "Emulsion E: High silver chloride tabular grain emulsion having a principal plane of {100}" (Comparative Example) 19.5 g of deionized alkali-treated bone gelatin having a methionine content of about 40 .mu.mol / g, 1N While stirring at a temperature of 40 ° C., a solution of 1582 ml of gelatin containing 7.8 ml of nitric acid and 13 ml of 10% sodium chloride was stirred at 1.1 ° C.
An 8M aqueous solution of silver nitrate and a 1.21M aqueous solution of sodium chloride were quantitatively added at a rate of 12.4 ml / min at 62.4 ml / min. 3
After stirring for 0.1 min, a 0.12 M aqueous silver nitrate solution and 0.12 M
28.2 ml of potassium bromide aqueous solution at 80.6 ml per minute
Each was added quantitatively. After stirring for 3 minutes, Solution 10 and Solution 11 were added at a constant amount of 46.8 ml at 62.4 ml / min, and after further stirring for 2 minutes, an aqueous gelatin solution containing 13 g of the above deionized alkali-treated bone gelatin and 1.3 g of sodium chloride (Adjust to pH 6.5 with sodium hydroxide)
Was added to adjust the pCl to 1.75, the temperature was raised to 63 ° C., and then hydrogen peroxide solution was added to 6 × 10 5
^-4 mol, pCl was further adjusted to 1.70, and
Aged for minutes. Thereafter, an AgCl fine grain emulsion (average grain diameter: 0.1 μm) was added at 2.68 × 10 ⁻² mol per minute for 20 minutes. After aging for 40 minutes after the addition was completed, a precipitant was added, the temperature was lowered to 35 ° C, and the precipitate was washed by settling and precipitation in a usual manner. Disperse gelatin was added and adjusted to pH 6.0 at 60 ° C.
Observation of a TEM image of a replica of the grain revealed that the obtained emulsion was a silver chloride {100} tabular grain containing 0.44 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows.

($ 10 with aspect ratio of 2 to 25)
0｝ total projected area of tabular grains / sum of projected areas of all AgX grains × 100 = a 1 = 95% (average aspect ratio of {100} tabular grains having an aspect ratio of 2 to 30 (average diameter / average thickness) )) = A2 =
10.0 (average diameter of {100} tabular grains having an aspect ratio of 2 to 30) = a3 = 1.40 μm (principal edge length ratio of {100} tabular grains having an aspect ratio of 2 to 30) = a4 = 0.90 (average thickness of {100} tabular grains having an aspect ratio of 2 to 30) = a5 = 0.09 μm (coefficient of variation (thickness of thickness distribution of {100} tabular grains having an aspect ratio of 2 to 30) Standard deviation / average thickness) = a
6 = 0.11 (Two dislocation lines extending from the corners of the {100} tabular grains having an aspect ratio of 2 to 25 are projected area / aspect ratio 2 to 25 of the grains that can be observed with a transmission electron microscope. The following {100} tabular grain projected area × 10
0) = a7 = 87 (average angle between two dislocation lines)
= A8 = 56 ° Further, when the tabular grains were observed by a direct TEM image, even in the emulsion after coating, the dislocation lines of the present invention could be observed in grains having a projected area of 57%.

"Emulsion F: High silver chloride tabular grain emulsion doped with compound (I-1) of the present invention and having {100} as a main plane" (Invention) 1 minute and 15 seconds before completion of addition of silver chloride fine particles (5% in silver
From the compound (I-1) of the present invention at a local concentration of 1
Emulsion J was prepared in exactly the same manner as Emulsion I except that 3 × 10 ^-4 mol was added per mol.

While stirring the obtained emulsions E and F, 5
Chemical sensitization was performed while maintaining the temperature at 6 ° C. First, thiosulfonic acid compound-I was added in an amount of 10 ^-4 mol per mol of silver halide, and then AgBr fine particles having a diameter of 0.10 μm were added in an amount of 1.0 mol% based on the total silver amount. KI
The solution was added in an amount of 10 ^-3 mol per mol of silver halide, and 3 minutes later, thiourea dioxide was added in an amount of 1 × 10 ^-6 mol per mol of silver halide, and held for 22 minutes to carry out reduction sensitization. . Next, 4-hydroxy-6-methyl-
1,3,3a, 7-Tetraazaindene was added in an amount of 3 × 10 ^-4 mol per mol of silver halide, and sensitizing dyes 1, 2, and 3 were added, respectively. Further calcium chloride was added.
Further, chloroauric acid was added in an amount of 1 × 10 5 per mol of silver halide.
^-5 mol and 3.0 × 10 ^-3 mol of potassium thiocyanate were added, followed by 6 × 10 ^-6 sodium thiosulfate.
And 4 × 10 ^-6 mol of selenium compound-I. After another 3 minutes, 0.5 g of nucleic acid was added per mole of silver halide. After 40 minutes, water-soluble mercapto compound-1 was added and the mixture was cooled to 35 ° C.

[0115]

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(Preparation of Emulsion Layer Coating Solution) The following chemicals were added per mole of silver halide to the chemically sensitized emulsion to prepare an emulsion coating solution.・ Gelatin (including gelatin in emulsion) 50.0 g

Dextran (average molecular weight 39,000) 10.0 g Sodium polyacrylate (average molecular weight 400,000) 5.1 g Sodium polystyrene sulfonate (average molecular weight 600,000) 1.2 g Iodide Potassium 78 mg Hardener 1,2-bis (vinylsulfonylacetamido) ethane Addition amount is adjusted so that the swelling ratio becomes a value of 90%. Compound E-1 42.1 mg Compound E-2 10.3 g Compound E-3 0.11 g Compound E-4 8.5 mg Compound E-5 0.43 g Compound E-6 0.04 g Compound E-7 70 g

[0118]

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Dye emulsion a (as dye solid content) 0.50 g

(Preparation of Dye Emulsion a) 60 g of Dye-1
62.8 g of 2,4-diamylphenol, 62.8 g of dicyclohexyl phthalate and ethyl acetate 3
33 g were melted at 60 ° C. Next, 65 cc of a 5% aqueous solution of sodium dodecylbenzenesulfonate and gelatin 9
4 g and 581 cc of water were added, and 60
The mixture was emulsified and dispersed at 30 ° C. for 30 minutes. Next, 2 g of methyl p-hydroxybenzoate and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, Asahi Kasei ultrafiltration lab module AC
Using P1050, concentrate until the total amount is 2 kg,
1 g of methyl p-hydroxybenzoate was added to obtain a dye emulsion a.

[0121]

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30 mg of Dye Emulsion m (as Dye Solids) (Preparation of Dye Emulsion m) 10 g of Dye-2 was weighed and dissolved in a solvent composed of 10 ml of tricresyl phosphate and 20 ml of ethyl acetate. , Anionic surfactant 750mg
Was emulsified and dispersed in 100 ml of a 15% aqueous gelatin solution containing the above to prepare a dye emulsion m.

[0123]

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(Adjustment to pH 6.1 with NaOH) (Preparation of Dye Layer Coating Solution) A coating solution was prepared so that each component of the dye layer had the following coating amount.・ Gelatin 0.25 g / m ²・ Compound E-8 1.4 mg / m ²・ Sodium polystyrene sulfonate (average molecular weight 600,000) 5.9 mg / m ²

[0125]

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Dye dispersion i (as dye solids) 20 mg / m ²

(Preparation of Dye Dispersion i) Dye-3 was handled as a wet cake without drying, and weighed to a dry solid content of 6.3 g. The dispersing aid V was treated as a 25% by weight aqueous solution, and was added so that the dry solid content was 30% by weight based on the solid content of the dye. Add water and add 6
3.3 g, and mixed well to form a slurry. 100 cc of beads made of zirconia having an average diameter of 0.5 mm are prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.) for 6 hours to give a dye concentration of 8% by weight. Water was added to obtain a dye dispersion. The resulting dispersant was mixed so that the solid content of the dye was 5% by weight and the photographic gelatin was equal to the solid content of the dye by weight.
An aqueous solution was added so as to have a concentration of 000 ppm, refrigerated, and stored in a jelly state. Thus, a dye dispersion i was obtained as a non-elutable solid fine particle dispersion dye having a light absorption maximum at 915 nanometers. The average particle diameter of the solid fine particles of the dye dispersion i was 0.4 μm.

[0128]

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[0129]

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(Preparation of Coating Solution for Surface Protective Layer) A coating solution for surface protective layer was prepared such that each component had the following coating amount. Gelatin 0.78 g / m ² Sodium polyacrylate (average molecular weight 400,000) 25 mg / m ² Sodium polystyrene sulfonate (average molecular weight 600,000) 1.2 mg / m ² Matting agent-1 (average particle size 3.7 μm) 72 mg / M ² matting agent-2 (average particle size 0.7 μm) 10 mg / m ²

[0131]

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[0132] Compound E-9 18mg / m ² Compound E-10 37mg / m ² Compound E-11 6.8mg / m ² Compound E-12 3.2mg / m ² Compound E-13 1.2mg / m ² Compound E-14 2.2 mg / m ² Compound E-15 30 mg / m ² Proxel 1.0 mg / m ² (adjusted to pH 6.8 with NaOH)

[0133]

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(Preparation of Support) (1) Preparation of Dye Dispersion B for Undercoat Layer The following Dye-4 was ball-milled by the method described in JP-A-63-197943.

[0135]

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434 cc of water and 6.7 of Triton X200® surfactant (TX-200®).
791 ml of a 1% aqueous solution was placed in a 2 liter ball mill. 20 g of the dye were added to this solution. 400 ml (2 mm diameter) beads of zirconium oxide (ZrO ₂ ) were added, and the contents were ground for 4 days. Thereafter, 160 g of 12.5% gelatin was added. After defoaming, Zr is filtered
O ₂ beads were removed. Observation of the obtained dye dispersion showed that the particle size of the crushed dye was 0.05 to 1.15 μm.
m, with an average particle size of 0.3
It was 7 μm. Further, the dye particles having a size of 0.9 μm or more were removed by centrifugation to obtain a dye dispersion d.

(2) Preparation of Support A corona discharge was carried out on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and the coating amount of the first undercoating liquid having the following composition was 4.9 ml / m ^2. At 185 ° C.
Dried for minutes. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained a dye-1 containing 0.04% by weight. Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 ml 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 ml distilled water 801 ml Contains 0.4 wt% of compound E-16 as an emulsifying dispersant based on the solid content of latex

[0138]

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(3) Coating of undercoat layer A second undercoat layer having the following composition was applied on the first undercoat layer on both sides of the above both sides one by one so that the coating amount would be as described below. 155 ℃ by wire bar coder
And dried.・ Gelatin 80 mg / m ²・ Dye dispersion B (as dye solid content) Coating amount in Table 1 ・ Compound E-17 1.8 g / m ²・ Compound E-18 0.27 g / m ²・ Mat agent average 2.5 g / m ^{2 of} polymethyl methacrylate having a particle size of 2.5 μm

[0140]

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(Preparation of photographic material) Prepared as described above
Combine the dye layer, emulsion layer and surface protective layer on the support
It was applied to both sides by the simultaneous extrusion method. Per side
The coated silver amount is 1.4 g / m ^TwoAnd

(Measurement of swelling ratio)
It is aged for 7 days at 0 ° C. and 60% RH. Next, this photosensitive material is immersed in distilled water at 21 ° C. for 3 minutes, and this state is frozen and fixed with liquid nitrogen. This photosensitive material is cut by a microtome so as to be perpendicular to the surface of the photosensitive material, and then freeze-dried at -90 ° C. Obtained products subjected to the above processing are observed with a scanning electron microscope to obtain a swollen film thickness Tw. On the other hand, the film thickness Td in a dry state is also obtained by cross-sectional observation using a scanning electron microscope. The value obtained by dividing the difference between Tw and Td thus obtained by Td and multiplying by 100 was defined as the swelling ratio (unit%).

(Preparation of Concentrated Developing Solution) Concentrated developing solution A having the following formulation and using sodium erythorbate as a developing agent was prepared.

Concentrated developer A Diethylenetriaminepentaacetic acid 8.0 g Sodium sulfite 20.0 g Sodium carbonate monohydrate 52.0 g Potassium carbonate 55.0 g Sodium erythorbate 60.0 g 4-hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 13.2 g 3,3'-diphenyl-3,3'-dithiopropionic acid 1.4 g diethylene glycol 50.0 g Compound E-19 0.15 g Compound E-20 0.3 g

[0145]

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Water is added to make up 1 liter. Adjust to pH 10.1 with sodium hydroxide.

(Preparation of developer replenisher)
It was diluted twice and used as a developing replenisher.

(Preparation of developing mother liquor) 2 liters of the above concentrated developing solution was diluted with water to 4 liters, and 55 ml of a starter solution having the following composition was added per liter of the diluted developing solution.
The developing solution of H9.5 was used as a developing mother liquor. (Preparation of starter solution) Potassium bromide 11.1 g Acetic acid 10.8 g Water was added to make up to 55 ml.

(Preparation of concentrated fixing solution) A concentrated fixing solution having the following formulation was prepared. Water 0.5 L Ethylenediaminetetraacetic acid dihydrate 0.05 g Sodium thiosulfate 200 g Sodium bisulfite 98.0 g Sodium hydroxide 2.9 g Adjust the pH to 5.2 with NaOH, and add water to make 1 L.

(Preparation of Fixing Replenisher)
It was diluted twice and used as a fixing replenisher.

(Preparation of fixing mother liquor) Two liters of the above concentrated fixing solution was diluted with water to make 4 liters. pH was 5.4.

(Washing water replenisher) Glutaraldehyde 0.3 g Diethylene-triamine-penta-acetic-acid 0.5 g Diluted with distilled water and adjusted to pH 4.5 with NaOH to obtain 1 liter of the finished solution. Was.

(Processing process of photographic material) CEPROS-S manufactured by Fuji Photo Film Co., Ltd. was modified, and according to the following process,
The washing layer was made into two-stage washing, and the second washing layer was supplemented with washing water. The aperture ratios of the developing layer and the fixing layer were improved to 0.02. The volume of the washing layer is 6 liters in each case.
In addition, a heat roller method was used for drying. Using the developing mother liquor, the fixing mother liquor and the rinsing water replenisher, the developing replenisher, the fixing replenisher and the rinsing water replenisher were mixed with 1 m ² of the photosensitive material.
The processing was carried out while replenishing 65 ml per bottle. Process temperature Processing time Current image 35 ° C 8 seconds Fixed 35 ° C 7 seconds Rinse 1st 30 ° C 5 seconds Rinse 2nd 25 ° C 5 seconds Dry 55 ° C 3 seconds Total 28 seconds

(Evaluation of photographic performance) The photographic material was exposed for 0.05 seconds from both sides using an X-ray orthoscreen HGM manufactured by Fuji Photo Film Co., Ltd. After the exposure, the sensitivity of the compound KIrCl ₄ (H ₂ O) ₂ (I-3) of the present invention was evaluated by evaluating the reciprocal of the ratio of the exposure amount giving a density of 1.0 in addition to fog based on the emulsion E. Good performance was obtained with the sample containing doped emulsion F.

Example 5 With respect to the emulsion containing silver iodobromide {111} tabular grains, the compound KIrCl ₄ (H ₂ O) of the present invention was added to 3% of the grain surface phase of Emulsion E of Example 2 of JP-A-6-258788. ) ₂ (I-
Emulsion was prepared in the same manner except that 3) was added at a local concentration of 10 ⁻³ mol / mol Ag, and sample 6 of Example 3 was prepared.
Except for using the fifth layer of the photosensitive material of (Sample No. 101), the same processing as in Example 1 gave good performance.

Example 6 With respect to the emulsion containing silver chloride {111} tabular grains, the grain surface phase of the emulsion of Example 2 in JP-A-8-227117 was 3%.
Emulsion was prepared and processed in the same manner except that the compound KIrCl ₄ (H ₂ O) ₂ (I-3) of the present invention was added at a local concentration of 10 ⁻³ mol / mol Ag to obtain good performance. Was.

Example 7 An emulsion containing silver chloride cubic grains was prepared according to the method described in JP-A-7-22.
In the same manner, the compound KIrCl ₄ (H ₂ O) ₂ (I-3) of the present invention was added at a local concentration of 10 ⁻³ mol / mol Ag to 3% of the grain surface phase of the emulsion D of Example 6 of No. 5445. When the emulsion was prepared and processed, good performance was obtained.

Example 8 An emulsion containing silver chlorobromide cubic grains was prepared as described in JP-A-8-2.
No. 11532, except that a local concentration of 10 ⁻³ mol / mol Ag of the compound KIrCl ₄ (H ₂ O) ₂ (I-3) was added to 3% of the grain surface phase of the emulsion E of Example 1 of Example 1. Preparation of the emulsion and treatment with a hydrazine nucleating agent gave better performance than the emulsion without the addition.

Example 9 An emulsion containing silver chlorobromide cubic grains was prepared as described in JP-A-8-2.
Emulsion according to the same method except that the compound KIrCl ₄ (H ₂ O) ₂ (I-3) of the present invention was added at a local concentration of 10 ⁻³ mol / mol Ag to 3% of the grain surface phase of the emulsion of Example 1 of No. 86311. Preparation and treatment with a hydrazine nucleating agent gave better performance than the emulsion without the addition.

[0160]

As is clear from the examples, the compounds of the present invention can produce highly sensitive silver halide photographic materials.

Claims (1)

[Claims] An iridium complex represented by the following general formula (I) is contained in a silver halide grain, and a localized phase having a concentration of the iridium complex which is at least 10 times higher than that of other parts is defined as 12 parts by volume of the grain. % Of silver halide photographic emulsion characterized by having a surface phase of not more than 10%. Formula (I) [IrX _p (H ₂ O) _m ] ⁿ wherein X represents a halogen, and p = 3, 4, or 5,
m = 6-p, n = 2-, 1- or 0.