JP2515129B2 - Silver halide photographic material - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material using an emulsion composed of silver halide grains having a novel structure and composition. Is.

(Prior Art and Its Deficiencies) With the recent trend toward small-format color films and diversification of shooting conditions, there has been a strong demand for films with ever increasing sensitivity and wide exposure suitability. Under these circumstances, high sensitivity, low fog and fine grain are further required for the basic performance of silver halide in the emulsion. These performances contribute to the progress of the entire silver halide light-sensitive material. It is desirable to reduce the inefficiency in the exposure process and increase the quantum sensitivity in the direction of producing an emulsion having high sensitivity and fine grain. Inefficiency factors related to quantum sensitivity include recombination, latent image dispersion, and competing electron traps derived from structural defects. Several attempts have been made to add an Fe compound during grain formation of silver halide. For example, Japanese Examined Patent Publication (Kokoku) No. 48-35373 describes that when a water-soluble iron compound is present in an amount of 10 ^-7 to 10 ^-3 mol per 1 mol of silver during grain formation, a high-contrast emulsion can be obtained without significant reduction in sensitivity. ing.

Japanese Patent Publication No. 53-31365 describes that the surface / internal sensitivity ratio is increased by adding a ferricyanide of an alkali metal to a precipitating agent at the emulsion preparation stage.

In Japanese Examined Patent Publication No. 49-14265, a silver halide grain having a grain size of 0.9 μm or less is added with a Group 8 metal compound at a concentration of 10 ⁻⁶ to 10 ⁻³ mol / mol Ag at the time of grain formation, and is further sensitized with a merocyanine dye. The prepared emulsion is said to have high sensitivity at high illuminance (10 ^-5 seconds or less). On the other hand, Fe ²⁺ ions can acquire holes in a silver halide crystal for a certain period of time, for example, see Physical Review Vol. 140, No. 2A No. 656 to 66.
See page 7 and The Journal of Chemical Physics, Vol. 65, No. 4, 1530 to 1538.

On the other hand, in the prior art described above, the photographic characteristics are found (or) added by adding the Fe ²⁺ compound at the time of grain formation, and the optimum addition amount is described. It is an important technique to improve the sensitivity of the emulsion to prevent recombination of holes and electrons generated during exposure and reaction of holes and latent images in a silver halide crystal which is a photosensitive recording material. These things are described in many documents, but if one example is shown,
Photographic Science Engineering No. 16
Volume 69 p. 1972, etc. In addition, when silver halides used in ordinary photographic light-sensitive materials are joined with different halogen compositions, it is considered that the difference in two different band gap energies mainly appears as the difference in energy level in the valence band. Therefore, if different halogen compositions are present in one grain, holes are likely to collect in the halogen composition portion having a small band gap energy. This is due to the Journal of Applied Physics, Vol. 60 (11) No. 1, pp. 3945-3953, and the Abstracts of the Annual Meeting of the Japan Photography Society 1987, A-.
It is mentioned in 11th mag.

The bandgap energy here means the difference between the highest energy level occupied by electrons and the lowest energy not occupied by electrons at absolute zero when considering the energy level of electrons in the wave number space in a solid crystal. The lowest energy when the wave numbers are equal is the band gap energy in the direct transition, and the lowest energy when the wave numbers are different is the band gap energy in the indirect transition. The general theory of these is detailed in the introductory books on solid-state physics, for example, in Chapter 7 of Charles Kittel's introduction To Solid State Physics 4th edition (John Willey and Lins, Inc.).

Therefore, it is effective to dope Fe ²⁺ to the portion of the halogen composition having the smallest bandgap energy in the grain in order to collect the holes in a more restricted place.
Examples of the halogen composition having a small band gap energy include silver iodide and silver iodobromide halogen compositions. They therefore have long-wave light absorption. Examples of the halogen composition having a large band gap energy include silver chloride and silver chlorobromide-based halogen compositions.

In the prior art, the water-soluble iron compound added during grain formation is not particularly limited and may be divalent or trivalent.

According to the present invention, the iron ion added must be a hole-trapping center doped in the silver halide, and therefore must be a divalent iron ion.

The addition of the water-soluble iron compound in the present invention must be done so as to dope the portion of the halogen composition having the smallest band gap in the grain.

The present inventors have found that satisfying such conditions leads to a surprising improvement in sensitivity.

(Object of the Invention) An object of the present invention is to provide a silver halide photographic material using a high-sensitivity emulsion in which the light absorption amount per grain is at least developable. The aim is to further increase the sensitivity of the emulsion.

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a photographic light-sensitive material having at least one silver halide emulsion layer on a support, and two or more halogen compositions in which one grain is different in the silver halide emulsion layer. from contain constituted photosensitive silver halide grains, the portion of the most bandgap energy smaller halogen composition of the silver halide grains, of the portion per mol of silver halide 10 ^-7 mol or more divalent It has been achieved by a silver halide photographic light-sensitive material characterized by containing iron ions.

The silver halide grains to which the present invention is applied are composed of two or more parts having different halogen compositions, each of which is composed of silver chloride, silver bromide, silver iodide or a mixed crystal thereof. Also, any combination may be used.

Particularly, as a halogen composition having a small band gap energy, a silver iodide type is preferable, and Fe is particularly preferable.
More preferably, the iodine content of the portion to which is added is 10 mol% or more.

The two or more portions having different halogen compositions may be core / shell emulsions, epitaxial grains, or grains having a multiple structure.

However, there must be at least two parts of different composition. The portion of the halogen composition having the smallest band gap energy may be any amount of the total halogen composition, but it is preferably 10% or more. The particles may be monodisperse or polydisperse. The shape of the grains may be cubic, octahedron, tetradecahedron, other polyhedrons, twins, flat plates, epitaxial grains,
Any of multi-structured particles and the like may be used.

Examples of water-soluble iron (divalent) compounds added to dope Fe ²⁺ include K ₄ [Fe (CN) ₆ ], FeCl ₂ and FeSO _4, but any water-soluble iron compound can be used. Good.

Further, the doping amount of these water-soluble iron compounds is preferably 1 × 10 ⁻⁷ mol or more per mol of silver halide. More preferably, it is 1 × 10 ⁻⁶ to mol or more. Particularly preferred is 3 × 10 ^{−6 to} 3 × 10 ⁻⁵ mol.

The doping amount with respect to the Fe silver halide is defined with respect to the silver halide amount of the halogen composition portion having the smallest band gap energy.

In the present invention, the addition of the iron compound is essential when forming the halogen composition portion having the smallest band gap energy in the grain. Further, after that, when the grains are grown with another halogen composition, it is more preferable to wash the emulsion once and remove the iron ions not doped in the grains.

The Fe compound thus doped in the silver halide grains can be quantitatively analyzed by using an analytical method such as atomic absorption spectroscopy. For example, when Fe ²⁺ is doped in the core part of the double structure grain, the core part is analyzed by etching only the shell part using a silver halide solvent such as KBr solution or sodium thiosulfate solution. The Fe ²⁺ content in can be determined. For example, when Fe ²⁺ is doped on the substrate side of the copitaxial particles, it is possible to selectively dissolve only the copy part by using the difference in the dissolution rate in the solvent due to the difference in the halogen composition and obtain the Fe content in the core part. it can.

 The combinations of different halogen compositions are listed.

For example, in the double-structured grain, if the core portion is silver iodobromide and the shell portion is silver bromide, the portion having the smallest band gap energy is the core portion. When the core portion is silver bromide and the shell portion is silver chlorobromide, the portion having the smallest band gap energy is the core portion. In the case of a multi-structure grain consisting of the following a, b and c parts, the b part has the halogen composition with the minimum band gap energy.

B. It is a central part consisting of AgBrI (I: 20 mol%) and occupies 60 mol% of the whole particles.

(B) An outer portion of (i) consisting of AgBrI (I: 38 mol%) and occupies 20 mol% of the whole particles.

(C) It is an outer part of B consisting of AgBrCl (Cl: 2 mol%) and occupies 20 mol% of the whole particle.

Further, in the case of the epitaxial grain composed of the following portions a, b and c, the portion a is the portion having the smallest band gap energy.

B. It is a central part composed of AgBrI (I: 30 mol%) and occupies 30 mol% of the whole particles.

(B) It is an outer part of (i) consisting of AgBr and occupies 60 mol% of the whole particles.

(C) Consists of AgBrCl (Cl: 70 mol%), and is a part localized in the corner part of B and occupies 10% of the whole particle.

The emulsion atmosphere at the time of adding the iron compound may be either a reducing atmosphere or an oxidizing atmosphere, but the reducing atmosphere is more effective.

Regarding the addition of the divalent water-soluble iron compound, it may be added at a constant rate or may be added all at once. It may be dissolved in a silver or halogen solution or may be added independently.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Ch.
imie et Physique Photographique Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry
(Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et.
al, Making and Coating Photographic Emulsion.Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, a one-sided mixing method, a simultaneous mixing method,
Any combination of them may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the above-mentioned legerar grains is
Obtained by controlling pAg and pH during particle formation.
For details, see, for example, Photographic Science and Eng.
ineering, Vol. 6, pp. 159-165 (1962);
Journal of Pho
Tographic Sciens), 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Pra
ctice (1930), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Pho
tographic Science and Engineering), Volume 14, 248-
257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,31
No. 0, 4,433,048, 4,439,520 and British Patent No.
It can be easily prepared by the method described in 2,112,157 and the like. The use of tabular grains has advantages such as an increase in covering power and an increase in color sensitization efficiency with a sensitizing dye, and they are described in detail in US Pat. No. 4,434,226 and the like.

Silver halide solvents are useful in promoting ripening.
For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, it is clear that mere introduction of a halide salt solution into the reactor can accelerate aging. Other ripening agents can be used, and the total amount of these ripening agents can be added to the dispersion medium in the reactor before the addition of silver and halide salts, or 1 or 2 or more. It is also possible to add the halide salt, silver salt or peptizer of the above and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. As described in JP-B-58-1410, Moisar et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions have internal grains during precipitation. Reduction sensitization can be performed.

In the present invention, it is important to carry out chemical sensitization represented by sulfur sensitization and gold sensitization. The location of chemical sensitization depends on the composition, structure, and shape of the emulsion grains, and on the intended use in which the emulsion is used. In some cases, the chemically sensitized nuclei are embedded in the grain, at a shallow position from the grain surface, or in some cases the chemically sensitized nuclei are formed on the surface.
Although it is also effective in the case of the effects of the present invention, it is particularly preferable to form a chemically sensitized nucleus near the surface. That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

Chemical sensitization is described by THJames, The Photographic Process, 4th Edition, Macmillan, 1977, (THJames, The Theory of the Photogra
Phic Process, 4 thed, Macmillan, 1977) with active gelatin as described on pages 67-76, and Research Disclosure, 120, 1974, April 12008; Research Disclosure, 34. Volume, 19
June 1975, 13452, U.S. Patent Nos. 2,642,361, 3,297,44
No. 6, No. 3,772,031, No. 3,857,711, No. 3,901,714,
4,266,018 and 3,904,415, and sulfur, selenium, tellurium, gold at pAg 5-10, pH 5-8 and temperature 30-80 ° C as described in British Patent No. 1,315,755.
It can be carried out using platinum, palladium, iridium or a combination of these sensitizers. Chemical sensitization is optimally carried out in the presence of gold and thiocyanate compounds and also in U.S. Pat. Nos. 3,857,711, 4,266,018 and 4,05.
Sulfur-containing compounds described in 4,457 are hypo,
It is carried out in the presence of a sulfur-containing compound such as a thiourea compound and a rhodanin compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. The chemical sensitization aids used include azaindene, azapyridazine, and azapyrimidine,
Compounds known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are U.S. Pat.Nos. 2,131,038 and 3,411,914,
No. 3,554,757, JP-A-58-126526 and the above-mentioned Daffin's "Photographic Emulsion Chemistry", pages 138-143.
In addition to, or as an alternative to, chemical sensitization, U.S. Pat.
As described in U.S. Pat.
2,518,698, 2,743,182 and 2,743,183 with stannous chloride, thiourea dioxide, polyamines and such reducing agents, or low pAg.
Reduction sensitization can be achieved by (eg less than 5) and / or high pH (eg greater than 8) treatment. Further, the color sensitization can be improved by the chemical sensitization method described in US Pat. Nos. 3,917,485 and 3,966,476.

Further, the chemical sensitization method described in JP-A-61-93453 is particularly effective when combined with the emulsion of the present invention.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose.

For more details on these additives, see Research Disclosure Item 17643 (December 1978) and Item 18716.
(November, 1979) and the relevant places are summarized in the table below.

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 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
Examples include -β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, hydrazine zincates, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives such as, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine -Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

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

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 3 or less per square meter of the light-sensitive material, and 500 ml can be obtained by reducing the bromide ion concentration in the replenishing solution.
It can also be: When the replenishment amount is reduced, it is preferable to prevent the evaporation of liquid and air oxidation by reducing the contact area of the treatment tank with air. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a method of performing bleach-fixing processing after bleaching processing may be used.
Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids,
Quinones, nitro compounds, etc. are used. Typical bleaching agents are ferricyanides; dichromates; iron (III)
Alternatively, cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-
Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. . Among these, new aminopolycarboxylic acid (III) including ethylenediaminetetraacetic acid iron (III) complex salt
Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
No. 8, JP-A-53-32,736, JP-A-53-57,831 and JP-A-53-37,
418, 53-72,623, 53-95,630, 53-95,63
No. 1, No. 53-10,4232, No. 53-124,424, No. 53-141,6
No. 23, No. 53-28,426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17,129 (July, 1978);
Thiozolidine derivatives described in No. 129; Japanese Examined Patent Publication No. 45-8,506
No., JP-A-52-20832, JP-A-53-32,735, U.S. Pat.
Thiourea derivatives described in 3,706,561; West German Patent 1,127,7
15, iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in British Patents 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836;
Other JP-A-49-42,434, JP-A-49-59,644, JP-A-53-9
No. 4,927, No. 54-35,727, No. 55-26,506, No. 58-16
Compounds described in 3,940; bromide ions and the like can be used.
Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-9
The compounds described in 5,630 are preferred. In addition, US Patent No.
The compounds described in 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the purpose, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage
Journal of the Society of Motion Picture and Telev
ision Engineers Vol. 64, pp. 248-253 (May 1955)
It can be determined by the method described in.

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium ions described in Japanese Patent Application No. 61-131,632,
The method of reducing magnesium ions can be used very effectively. Further, isothiazolone compounds and siabendasols described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9 and preferred is 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds-10 minutes at 15-45 ° C, preferably 30 seconds-5 minutes at 25-45 ° C. The range is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, all known methods described in JP-A-57-8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

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 it, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.Nos. 3,342,597, 3,342,599, Schiff base type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and U.S. Pat. And urethane compounds described in JP-A-53-135,628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-type light-sensitive materials for the purpose of promoting color development, if necessary.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A Nos. 56-64,339, 57-144,547, and 58.
-115,438 etc. are described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing 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.

(Example) Example 1 The following emulsions A, B, C and D were prepared, and the emulsions of the present invention and comparative emulsions having an average grain size of 1.5 μm and double structure grains were prepared by the following operations. made.

(Solution A) H ₂ O 1000 cc Gelatin 20 g KI 12 g NH ₄ NO ₃ 7.5 g NH ₃ 7.5 g (Solution B) AgNO ₃ 120 g H ₂ O 625 cc (Solution C) KBr 85 g H ₂ O 425 cc (Solution D) K ₄ [Fe (CN) ₆ ] H ₂ O D-10 100cc D-2 0.00007g 100cc D-3 0.007g 100cc D-4 0.02g 100cc Solution A stirred at 70 ° C B and C were added to form particles. During the first 5 minutes, Solution B was added at a rate of 30.3 cc / min and Solution C was added at a rate of 24.3 cc / min. At the same time, Solution D was added at a rate of 20 cc / min. After that, over a period of 40 minutes, solutions B and C were each 12.5 cc / min,
It was added at a rate of 8.2 cc / min. After the addition was completed, the emulsion was subjected to a normal desalting / redispersion step and then second-ripened.
Emulsions were added solutions D-1, D-2, D-3, D-4.
According to Em-1, Em-2, Em-3, and Em-4. And _{Na 2 S 2 O 3 · 5H} 2 O in the beginning of the ripening during chemical sensitization, KAuCl ₄ · 4H ₂ O
Was added optimally. The aging temperature at this time is 60 ° C., and the time is 60 minutes. After this, the emulsion and protective layer were coated on the triacetate film support in the coating amounts shown in Table 1.

Table 1 (1) Emulsion layer Emulsion ... Em-1 to 4 (silver 1.0 × 10 ^-2 mol / m ² ) (2) Protective layer 2,4-dichlorotriazine-6-hydroxy-s-triazine sodium salt (0.08) g / m ² ) Gelatin (1.80 g / m ² ) These samples were left under the conditions of 40 ° C and 70% relative humidity for 14 hours, then exposed for sensitometry and subjected to the next color development processing. .

The density of the treated sample was measured with a green filter. The obtained photographic performance results are shown in Table 2.

 The developing treatment used here was carried out at 38 ° C. under the following conditions.

1. Color development ………… 2 minutes 45 seconds 2. Bleach ………… 6 minutes 30 seconds 3. Washing ……… 3 minutes 15 seconds 4. Settling ……… 6 minutes 30 seconds 5. Washing …… 3 minutes 15 seconds 6. Stability 3 minutes 15 seconds The composition of the treatment liquid used in each process is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4- (N-ethyl-N-β hydroxyethylamino)-
2-Methyl-aniline sulfate 4.5 g Water added 1 Bleach Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium salt 130 g Glacial acetic acid 14 ml Water added 1 Fixer Tetrapolyline Sodium acid salt 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added to 1 stabilizing solution Formalin 8.0 ml Water was added 1 Exposure was performed at 1/100. About Em-1 to 4 Emulsion E
The sensitivity of m-1 was set to 100. Sensitivity is 0 with fog + optical density.
In terms of 2 Compared. As can be seen from Table 2, when a divalent water-soluble iron compound is added to the high iodine phase of the core in a molar ratio of 10 ^-7 to the silver halide, it is extremely effective.

The amount of Fe incorporated in the grains of Emulsions 1 to 4 was determined by atomic absorption spectroscopy. The results are shown in Table 3. The sample was subjected to repeated centrifugation to separate silver halide grains from gelatin and the like.

It can be seen that the doping rate of Fe in the silver halide crystals in this emulsion is several percent.

Comparative Example (Shell Dope) In the particle preparation process shown in Example 1, the solution D containing the iron compound was not used for the first 5 minutes of particle formation, but for the subsequent 40 minutes of particle shell formation. It was added for 30 minutes at the addition rate of 3.3 cc / min from the minute to the end of the addition 40 minutes later. The emulsion thus prepared was coated in the same manner as in Example 1 and subjected to sensitometry. The conditions are exactly the same as in Example 1. Solution D _{1 to} D ₄
For each emulsion added with, the sample name was Em-5, 6, 7,
8 Table 4 shows the relative sensitivity when the sensitivity of Em-5 at 1/100 second exposure is 100.

As is clear from Table 4, when the iron compound is added when growing the AgBr phase having a large band gap, the feeling becomes low.

Example 2 (Effect of water washing) In the sample preparation process shown in Example 1, water-soluble iron that was not incorporated into silver halide grains in the solvent was obtained by adding the solution D containing the iron compound and then performing the water washing process. The compound was removed. In this case, the emulsion name is Em-9, 1
The numbers are 0, 11, and 12. The sensitivity of Em-9 at 1/100 second exposure is 100
Table 5 shows the relative sensitivity.

Example (in the case of red blood salt) 3 An emulsion was prepared according to the emulsion preparation method described in Example 1. The following solution E was used in place of the divalent water-soluble iron compound shown in solution D. .

(Solution E) K ₄ [Fe (CN) ₆ ] H ₂ O E-10 100cc E-2 0.00007g 100cc E-3 0.007g 100cc E-4 0.02g 100cc According to Example 1, the emulsion contains an iron compound. After the core high iodine phase was grown while adding, a water washing step was performed for the purpose of removing the water-soluble iron compound remaining outside the silver halide grains before growing the shell.

After gold and sulfur sensitization were optimally carried out in the same manner as in Example 1, coating was carried out and sensitometry was carried out. The results are shown in the table.

As is clear from Table 6, the sensitivity of the emulsion is lowered with the trivalent water-soluble iron compound.

Example 4 A sample which is a multi-layer color light-sensitive material consisting of each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) For the coating layer, the amount of silver halide, colloidal silver and coupler is expressed in g / m ² unit of silver, and for the sensitizing dye, the mol per mol of silver halide in the same layer. It is shown by the number.

First layer: Antihalation layer Black colloidal silver Silver coverage 0.2 Gelatin 2.2 UV-1 0.1 UV-1 0.2 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 Second layer: Intermediate layer Fine grain silver bromide (Equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 1.0 Cpd-2 0.2 Third layer: First red emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent sphere diameter)
0.7μ, coefficient of variation of equivalent spherical diameter 14%, tetradecahedral grains) Silver coating amount 0.26 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter)
0.4μ, variation coefficient of equivalent spherical diameter 22%, tetradecahedral grain) Silver coating amount 0.2 Gelatin 1.0 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 0.4 × 10 ^-4 mol ExS -4 0.3 x 10 ^-4 mol ExC-1 0.33 ExC-2 0.009 ExC-3 0.023 ExC-6 0.14 4th layer: second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type, sphere) Equivalent diameter 1.
0Myu, sphere variation coefficient of 25% equivalent diameter, the plate-like particles, diameter / thickness ratio 4.0) silver coverage 0.55 Gelatin ^{0.7 ExS-1 3 × 10 -4} ExS-2 1 × 10 -4 ExS-3 0.3 × 10 - ⁴ ExS-4 0.3 × 10 ^-4 ExC-6 0.08 ExC-3 0.05 ExC-4 0.10 Fifth layer: third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, sphere equivalent) Diameter
Example 1 with 1.5 μ, variation coefficient of equivalent spherical diameter of 32%, plate-like particles, diameter / thickness ratio 6.0) Em-1 or Em-3 silver coating amount 0.9 gelatin 0.6 ExS-1 2 × 10 ⁻⁴ ExS− 2 0.6 × 10 ^-4 ExS-3 0.2 × 10 ^-4 ExC-4 0.07 ExC-5 0.06 Solv-1 0.12 Solv-2 0.12 6th layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 7th layer: 1st green feeling Emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter)
0.7μ, variation coefficient of spherical equivalent diameter 14%, tetradecahedral grain) Silver coating amount 0.2 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter)
0.4μ, variation coefficient of equivalent spherical diameter 22%, tetradecahedral grain) Silver coating amount 0.1 Gelatin 1.2 ExS-5 5 × 10 ^-4 ExS-6 2 × 10 ^-4 ExS-7 1 × 10 ^-4 ExM-1 0.41 ExM-2 0.10 ExM-5 0.03 Solv-1 0.2 Eighth layer: second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent spherical diameter 1.0 μ, variation coefficient of equivalent spherical diameter 25 %, Plate-like particles, diameter /
Thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.35 ExS-5 3.5 × 10 ^-4 ExS-6 1.4 × 10 ^-4 ExS-7 0.7 × 10 ^-4 ExM-1 0.09 ExM-3 0.01 Solv-1 0.15 9th layer: Intermediate layer Gelatin 0.5 10th layer: 3rd green emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter)
1.5μ, coefficient of variation of equivalent spherical diameter 32%, plate-like particles, diameter / thickness ratio 6.0) Em-1 or Em-3 silver coating amount of Example 1.0 Gelatin 0.8 ExS-5 2 × 10 ^-4 ExS- 6 0.8 × 10 ^-4 ExS-7 0.8 × 10 ^-4 ExM-4 0.04 ExM-3 0.01 ExC-4 0.005 Solv-1 0.2 11th layer: Yellow filter layer Cpd-3 0.05 Gelatin 0.5 Solv-1 0.1 12th layer : Intermediate layer Gelatin 0.5 Cpd-2 0.1 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, sphere equivalent diameter 0.7μ, sphere equivalent diameter variation coefficient 14%, 14 Hedron grains) Silver coating amount 0.1 Silver iodobromide emulsion (AgI 4.0 mol%, internal high iodine type, spherical equivalent diameter 0.4 μ, variation coefficient of spherical equivalent diameter 22%, tetrahedral grains) Silver coating amount 0.05 Gelatin 1.0 ExS -8 3 × 10 ^-4 ExY-1 0.53 ExY-2 0.02 Solv-1 0.15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, variation of equivalent spherical diameter 16%, tetradecahedral grain) Silver coating amount 0.19 Gelatin 1.3 ExS-8 2 × 10 ^-4 ExY-1 0.22 Solv-1 0.07 15th layer: Intermediate layer Fine grain silver iodide (AgI 2 mol) %, Uniform type, sphere equivalent diameter 0.13
μ) Silver coating amount 0.2 Gelatin 0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, equivalent sphere diameter)
Em-1 'or Em-3' silver coating amount with increased internal iodine content based on Example 1 of 1.5 μ, variation coefficient of equivalent spherical diameter of 32%, plate-like particles, diameter / thickness ratio 5.0) 1.0 Gelatin 0.5 ExS-8 1.5 × 10 ^-4 ExY-1 0.2 Solv-1 0.07 17th layer: 1st protective layer Gelatin 1.8 UV-1 0.1 UV-2 0.2 Solv-1 0.01 Solv-2 0.01 18th layer: 1st 2 Protective layer Fine grain silver bromide (sphere equivalent diameter 0.07μ) Silver coating amount 0.18 Gelatin Polymethylmethacrylate particles (diameter 1.5μ) 0.2 W-1 0.02 H-1 0.4 Cpd-5 1.0 The photographic element was exposed to 25 CMS using a tungsten light source with a filter adjusted to a color temperature of 4800 ° K, and then developed at 38 ° C according to the following processing steps.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each process is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5g Water added 1.0 pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water added 1.0 pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water is added 1.0 pH6.6 Stabilizer Formalin (40%) 2.0ml Polyoxy Ethylene-p-mononophenyl ether (average degree of polymerization 10) 0.3 g Water was added 1.0 Samples 6 using Emulsions Em-3 and Em-3 'of the present invention
1 is sample 6 using comparative emulsions Em-1 and Em-1 '.
-2, it was confirmed that the sensitivity was high and the reciprocity law property was improved. This example shows that the present invention is extremely effective also in a multilayer color light-sensitive material.

Claims (1)

(57) [Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein one grain in each silver halide emulsion layer is composed of two or more different halogen compositions. Functional silver halide grains, and in the portion of the halogen composition having the smallest band gap energy of the silver halide grain, 10 ⁻⁷ mol or more of divalent iron ion is contained per 1 mol of silver halide in the portion. A silver halide photographic light-sensitive material characterized by the above.