JPH0433020B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material. Generally, silver halide photographic materials are required to have various properties. For example, a negative photosensitive film and a negative photographic paper need to have good compatibility of characteristic curves with each other, that is, they need to have good gradation. Further, positive light-sensitive materials also need to have good gradation properties in order to improve tone reproducibility or color reproducibility. On the other hand, it is known that the above-mentioned photographic properties of silver halide photographic materials used by those skilled in the art vary depending on the conditions of the processing solution and processing equipment during development, and permanent improvement is desired. However, no effective means to solve this problem are known. Therefore, an object of the present invention is to provide a silver halide photographic material with good gradation. An object of the present invention is to provide a silver halide photographic light-sensitive material with significantly reduced fluctuations in photographic properties due to fluctuations in development processing, that is, improved processing stability. The above purpose is to contain at least 40 mg/100 g of silver of a water-soluble compound consisting of an element in a group of the Periodic Table of Elements and having a molecular weight of 100 or more, and further contain a black and white silver halide developing agent of 1.2 to 120 mg/100 g silver.
It has been found that this can be achieved by using a silver halide photographic material containing mg of silver halide. The water-soluble compound (hereinafter referred to as a compound of a group element) which is a compound consisting of an element in a group of the Periodic Table of the Elements and has a molecular weight of 100 or more is preferably ruthenium or rhodium in the 5th or 6th period. , salts of metals such as palladium, osmium, iridium and platinum. Representative compounds include the following compounds. (1) Ammonium chloroparadate (2) Potassium chloroplatinate (3) Sodium chloroplatinate (4) Ammonium chloroplatinate (5) Sodium chloroparadite (6) Ammonium hexachloroparadate () (7) Potassium hexachloroplatinate Date () (8) Sodium hexachloroiridate () (9) Ammonium hexachloroosmate () (10) Rhodium trichloride (11) Potassium hexachlororodate (12) Sodium hexachlororodate (13) Diaminopalladium chloride (14) Sodium Hexachloroplatinate (2009) More preferred compounds of group elements according to the present invention include salts of rhodium, iridium and platinum. Compounds of these group elements contain 40% per 100g of silver.
It is contained in the photographic material in an amount of 40 mg to 500 mg per 100 g of silver. The group element compound used in the present invention is preferably added to the photographic emulsion constituting the light-sensitive material as an aqueous solution. In this case, the concentration of the aqueous solution is 0.01.
It can be used in a range of 10% by weight. The group element compound used in the present invention may be added to the silver halide emulsion during or before chemical ripening, or during the preparation of silver halide grains. The effects of the present invention can only be achieved by incorporating a black and white silver halide developing agent into the silver halide photographic light-sensitive material in addition to the compound of the above-mentioned group elements. The black-and-white silver halide developing agent (hereinafter referred to as black-and-white developing agent) according to the present invention refers to a silver halide reducing compound, which generally performs a coupling reaction with a color coupler to form an image dye. It is distinguished from the main drug (e.g. aromatic amine derivatives). Any known black and white developing agent can be used in the present invention. A specific example is shown below. One specific example is a 3-pyrazolidone compound. For example, (15) 1-phenyl-3-pyrazolidone (16) 1-p-tolyl-3-pyrazolidone (17) 5-phenyl-3-pyrazolidone (18) 5-methyl-3-pyrazolidone (19) 1-phenyl -5-Methyl-3-pyrazolidone (20) 1-acetamidophenyl-3-pyrazolidone (21) 1-phenyl-4,4-dimethyl-3-pyrazolidone (22) 1-p-tolyl-4,4-dimethyl -3-
Pyrazolidone (23) 1-phenyl-4-methyl-3-pyrazolidone (24) 4-hydroxy-4-methyl-1-phenyl-3-pyrazolidone (25) 4-hydroxymethyl-4-methyl-1-
Examples include phenyl-3-pyrazolidone. Another specific example is a hydroxybenzene compound. For example, (26) hydroquinone (27) catechol (28) pyrogallol (29) N-methyl-p-aminophenol (30) p-β-hydroxyethylaminophenol (31) p-ethylaminophenol (32) N-methyl -N-(β-sulfamidoethyl)-p-aminophenol and the like. Other useful black and white developing agents include ascorbic acid and p-hydroxyphenylglycine. These black and white developing agents are 1.2 to 120 mg/100 silver.
It is preferably contained in the photosensitive material within the range of 11
Contained in the range of ~110mg. The black and white developing agent used in the present invention may be added to the silver halide emulsion constituting the silver halide light-sensitive material by any method, but it is preferably added as a solution in a solvent such as water or alcohol. The concentration of the solution can range from 0.01% to 10% by weight. The black and white developing agent used in the present invention may be added to the photographic emulsion at or before chemical ripening. The group element compound and black-and-white developing agent according to the present invention exhibit the effects of the present invention if they are contained in a silver halide photographic light-sensitive material, but the present invention is applied to a silver halide color photographic light-sensitive material. In some cases, it is preferable that both of the above-mentioned compounds are contained in a photosensitive unit having the same color sensitivity. However, even in this case, it is not necessarily necessary to contain both of the above-mentioned compounds in a photosensitive unit having the same color sensitivity. The selection may be made arbitrarily. As the silver halide emulsion used in the silver halide photographic material of the present invention, any silver halide emulsion used in the art can be used.
For example, it may contain crystals of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide, or a mixture of these crystals. The silver halide emulsion may be large grain or small grain, and monodisperse or polydisperse. Further, the silver halide crystal may be cubic, octahedral, epitaxial hybrid crystal, or the like. The emulsion can be a negative emulsion or a direct positive emulsion. They are mainly surface latent image type emulsions that form latent images on the surface of silver halide grains, internal latent image type emulsions that form latent images inside silver halide grains, or surface latent image type emulsions and internal latent image type emulsions. A mixture of can be used. The silver halide photographic material according to the present invention may contain a photosensitive dye for spectral sensitization or the like, and any dye can be used depending on the purpose. For example CEK
Mies, T.H. James, “The Theory.”
'Of the Photographic Process' (3rd edition), 1966 Macmillan Co., NY, p. 198~
Examples include cyanine dyes, merocyanine dyes, and xanthene dyes described on page 228. The binder for the silver halide photographic material of the present invention includes gelatin, colloidal albumin,
Cellulose derivatives such as agar, gum arabic, alkyl acids, hydrolyzed cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, etc., and synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-
N,-vinylpyrrolidone, other water-soluble polymers,
Gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin, and gelatin graft copolymerized with polymerizable ethylene group-containing monomers such as acrylic acid (ester), methacrylic acid (ester), and acrylonitrile. can be given. These binders can be used as needed.
Can be used as a compatible mixture of two or more. The silver halide emulsion used in the silver halide photographic material of the present invention can be sensitized with a chemical sensitizer. Chemical sensitization using noble metal sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers can be advantageously used in combination with the silver halide emulsion of the present invention. The above-mentioned silver halide emulsion may contain a stabilizer. Stabilizers useful in the present invention include the following: One of the effective methods is a nitrogen-containing heterocyclic compound.
For example, 4-oxo-6-thiono-4,5,6,
These include 7tetrahydro-1-thia-3,5,7-triacindene, 2-substituted benzimidazole, benzotriazole, substituted 1,2,3-triazole, urazole, pyrazole, tetrazole compound, polyvinylpyrrolidone, and the like. Polyvinylpyrrolidone is particularly useful in the present invention. Also useful in the present invention are quaternary ammonium salts. For example, thiazolium compounds and pyrylium compounds are useful. Among them, benzothiazolium compounds are particularly effective. Mercapto compounds are also useful as well.
For example, 5-phenyl-1-mercaptotetrazole, 2-mercapto-benzothiazole, 2-mercaptothiazole, mercaptobenzimidazole, mercaptooxadiazole, mercaptothiadiazole, thioshiyuga, 4-thiouracil and the like are effective. Among these, particularly useful ones include 5-phenyl-1-mercaptotetrazole and 2-mercaptobenzothiazole. Also useful are polyhydroxybenzene compounds. For example, 1,2-dihydroxybenzene compounds, gallic acid esters (eg, isoamyl gallate, dodecyl gallate, brobyl gallate) and 2-alkyl-hydroquinone are effective. Also, thione compounds such as thiazoline-2-
Thione compounds are also useful. Salts such as Zn and Cd are also useful. Also useful are tetrasindene compounds.
For example, 4-hydroxy-6-methyl-1,3,
3a,7-tetrasaindene, 4-methyl-6-
Hydroxy-1,3,3a,7-tetrazaindene, 4-hydroxy-5,6-dimethyl-1,
3,,3a,7-tetracindene and the like are useful. In the present invention, the stabilizers useful for inclusion in the silver halide photographic emulsion are as described above, but for example, they may be used in combination to achieve a more preferable stabilizing effect. Hardening of the emulsion is carried out according to conventional methods. The hardeners used are conventional photographic hardeners, such as aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, and their acetals, or derivative compounds such as sodium bisulfite adducts; methanesulfonic acid ester compounds. Mucochloric acid or mucohalogen acid compounds; Epoxy compounds; Aziridine compounds; Active halogen compounds; Maleic acid imide compounds; Active vinyl compounds; Carbodiimide compounds; Isoxazole compounds; N-methylol compounds; Isocyanates Compounds include inorganic hardeners such as chromium alum and zirconium sulfate. The silver halide photographic material of the present invention may contain a surfactant alone or in combination. The silver halide photographic material of the present invention includes an anti-static agent, a plasticizer, a fluorescent brightener, a development accelerator,
It may also contain air antifoggants, color toning agents, and the like. The silver halide photographic material of the present invention may contain any known dye-forming coupler for forming a color image. In many cases, it is desirable that the coupler have a structure in which it remains in a specific layer and does not diffuse into other layers during the manufacturing process, storage of the silver halide photographic light-sensitive material, and processing process. The coupler may be either 4-equivalent or 2-equivalent. It may also be a colored coupler for color correction, a colorless coupler, or a coupler that releases a development inhibitor during development (so-called DIR coupler). As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 2875057, No. 3408197, No. 3551155, No. 3582322, No. 3894875, West German patent publication
No. 1547868, West German patent application (OLS) No. 2213461,
There are those described in No. 2261361, No. 2263875, No. 2414006, etc. As magenta couplers, 5-pyrazolone compounds are mainly used, but indazolone compounds and cyanoacetyl compounds are also used. Examples are U.S. Patent Nos. 2,600,788, 3,062,653,
No. 3127269, No. 3311476, No. 3419391, No. 3519429, No. 3558319, No. 3582322,
West German Patent Application No. 3615506, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665, West German Patent Application No. 2418959,
It is described in No. 2424467, Japanese Patent Publication No. 40-6031, No. 44-2016, etc. Phenol or naphthol derivatives are mainly used as cyan couplers. Specific examples include US Patent No. 2369929, US Patent No. 2474293, and US Patent No.
2521908, 2895826, 3034892, 3386830, 3458315, 3476563,
No. 3583971, No. 3591383, JP-A-48-
There is one listed in 78905. In addition, a development inhibitor-releasing coupler (so-called DIR coupler) or a compound that releases a development-inhibiting compound during the coloring reaction can also be added. Examples of these are U.S. Pat. No. 3,227,554;
No. 3632345, No. 3701783, No. 3790384, British Patent No. 953454, West German Patent Application (OLS)
No. 2414006, No. 2417914, No. 2454301, No. 2414006, No. 2417914, No. 2454301, No.
2454329, U.S. Patent No. 3297445, U.S. Patent No. 3379529
No., JP-A-54-145135, JP-A-56-137353
It is stated in the issue bulletin etc. The silver halide photographic material according to the present invention may contain a colored coupler for color correction. Two or more types of the couplers mentioned above can be used in the same layer in order to satisfy the characteristics required for silver halide photographic materials, and the same compound can of course be added to two or more different layers. No problem. These couplers are generally dispersed in the silver halide emulsion layer with a solvent of appropriate polarity. Useful solvents include tri-o-cresyl phosphate, trihexyl phosphate, dioctyl butyl phosphate, di-butyl phthalate, diethyl laurylamide, 2,4-diallylphenol, octyl benzoate, and the like. Furthermore, various photographic additives other than those mentioned above may optionally be added to the silver halide photographic material according to the present invention. Silver halide photographic materials to which the present invention can be applied include, for example, color and black-and-white positive films, color and black-and-white paper sensitive films, color and black-and-white negative films, color and black-and-white reversal films (which may contain couplers), and plate-making materials. Photographic materials (e.g. gravure film)
m ² ), photosensitive materials for cathode ray tube displays, photosensitive materials for X-ray recording, colloids, transfer processes (e.g. described in U.S. Pat. No. 2,716,059), silver salt diffusion transfer processes (e.g., U.S. Pat. No. 2,352,014). , No. 2543181, No. 3020155,
No. 2,861,885), color diffusion transfer processes (e.g., U.S. Pat. No. 3,087,817,
Same No. 3185567, Same No. 2983606, Same No. 3253915,
Same No. 3227550, Same No. 3227551, Same No. 3227552,
It is described in the same No. 3415644, the same No. 3415645, the same No. 3415646, etc. ) die transfer process (described in, for example, US Pat. No. 2,882,156), and the like. Hereinafter, the present invention will be explained in more detail with reference to Examples, but the technical scope of the present invention is not limited by the following Examples, and various embodiments are possible. . Example 1 Silver iodide prepared by the double jet method was
A high-sensitivity silver iodobromide emulsion containing mol% was subjected to gold sensitization and sulfur sensitization, and then divided, and 1 kg of this emulsion (containing 1 mol of silver halide) was used to prepare the group element compound according to the present invention and black and white. Each developing agent was added as an aqueous solution as shown in Table 1. After adding mucochloric acid and saponin, coating on a cellulose triacetate-based support,
A sample was prepared by drying. For each of these samples, two strips were prepared and, after wedge exposure, one part was treated with developer (A) having the following composition and the other part with developer (B) at 30°C.
After developing for 2 minutes, fixing and washing were performed. Developer (A) Monobatol 3.5g Anhydrous sodium sulfite 40g Hydroquinone 7.0g Sodium carbonate 30g Potassium bromide 1.0g Add water to 1 and adjust the pH to 10.2. Developer (B) Same as developer (A), but adjust the pH to 11.0. Characteristic curves were examined for the obtained silver image, and sensitivity, gamma value, and fog were determined. The sensitivity was determined from the amount of exposure necessary to give an optical density of "fog + 0.1" and was expressed as a relative value, with the sensitivity when processed with the control developer (A) being 100.
The results are shown in Table 1.

【table】

[Table] As is clear from Table 1, it can be seen that the samples according to the present invention exhibit significantly smaller variations in photographic properties due to variations in development processing than the comparative samples. Example 2 Silver iodide prepared by the double jet method was
A high-sensitivity silver iodobromide emulsion containing mol% was subjected to gold sensitization and sulfur sensitization, and then divided, and 1 kg of this emulsion (containing 1 mol of silver halide) was used to prepare the group element compound according to the present invention and black and white. Developing agents were added as aqueous solutions as shown in Table 2. On the other hand, 80 g of α-pivalyl-4-(4-benzyloxyphenylsulfonyl)phenoxy-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide was added to tricresyl phosphate. of ethyl acetate and 100ml of
The mixture was completely dissolved in 50 ml of the mixed solution, and 2 g of sorbitan monolaurate was further added. This solution was added to 1 kg of a 10% by weight gelatin aqueous solution containing 2.5 g of dodecylbenzenesulfonic acid, stirred at high speed, and further subjected to ultrasonic stirring to obtain an emulsion. This emulsion
A sample was prepared by adding 400 g to the above photographic emulsion, further adding a hardening agent and a spreading agent, and coating the mixture on a cellulose triacetate base support and drying. For each of these samples, two strips were prepared, and after wedge exposure, one part was prepared with developer (C) having the following composition, and one part was prepared with developer (D) at 37.8%.
After developing for 3 minutes and 15 seconds at .degree. C., the following treatments were carried out. Bleaching...6 minutes 30 seconds Washing...3 minutes 15 seconds Fixing...6 minutes 30 seconds Washing...3 minutes 15 seconds Stabilization...1 minute 30 seconds Drying Treatment solutions used in each treatment step The composition is as follows. Developer (C) 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/2 sulfate 1.98g Sulfuric acid 0.74g Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitrilotriacetic acid trisodium salt (monohydrate) 1.20g Potassium hydroxide 1.48g Add water to make 1, Adjust to PH10.0. Developer (D) [Same as developer (C) or adjust pH to 10.5. Bleach solution Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1, and adjust the pH using ammonia water.
Adjust to 6.0. Fixer Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1, and adjust to PH6.0 using acetic acid. Stabilizing liquid Formalin 1.5ml Konidax 7.5ml (manufactured by Konishiroku Photo Industry Co., Ltd.) Add water to make 1. The characteristic curve of the obtained yellow image was examined, and the sensitivity, gamma value, and fog were determined. As in Example 1, the sensitivity was expressed with the sensitivity when processed using the control developer (C) as 100.
The results are shown in Table 2.

[Table] As is clear from Table 2, it can be seen that the samples according to the present invention have significantly smaller fluctuations in photographic properties due to fluctuations in development processing than the comparative samples, and at the same time have good gradation. Example 3 A sample was prepared in the same manner as in Example 2, but in this example, the silver iodobromide emulsion of Example 2 was orthosensitized, and 1-(2,4,6-trichlorophenyl) was used as the coupler. )-3-[3-(2,4-di-t-aminophenoxyacetamide)benzamide]-
5-pyrazolone was used. The sample was then exposed to green light and processed as in Example 2. The characteristic curve of the obtained magenta image was examined, and the sensitivity, gamma value, and fog were determined. The results were the same as in Example 2, and it was found that the fluctuations in photographic properties due to fluctuations in development processing were extremely small, and at the same time, the gradation was good. Example 4 A sample was prepared in the same manner as in Example 2, but in this example, the silver iodobromide emulsion of Example 2 was panchromatically sensitized, and 1-hydroxy-N-[γ
-(2,4-di-t-amylphenoxypropyl)-2-naphthamide was used. The sample was then exposed to red light and processed as in Example 2. Regarding the obtained cyan image, the characteristic curve was examined to determine the sensitivity, gamma value, and fog. The results were the same as in Example 2, and it was found that the fluctuations in photographic properties due to fluctuations in development processing were extremely small, and at the same time, the gradation was good. Furthermore, the sample prepared above was exposed to red light and processed in the same manner as in Example 2. However, the temperature of the developer (C) should be adjusted from 37.8℃ to 38.3℃.
The same process was carried out using developer (C) (all other conditions were the same as in Example 2). The characteristic curve of the obtained cyan image was examined, and the sensitivity, gamma value, and fog were determined. The results were similar to those of Example 2, and it was found that the samples according to the present invention had extremely small fluctuations in photographic characteristics due to such fluctuations in development processing, and at the same time had good gradation. Example 5 Silver iodide prepared by the double jet method was
A low-sensitivity silver iodobromide emulsion containing mol % is subjected to gold sensitization and sulfur sensitization, and then divided, and 1 kg of this emulsion (containing 1 mol of silver halide) is used to prepare the group element compound and/or Black and white developing agents were added as aqueous solutions as shown in Table 3. On the other hand, α-(4-carboxyphenoxy)-α-
Completely dissolve 160 g of pivaloyl-2-chloro-5-[α-(3-pentadecyphenoxy)butyramide] acetanilide in a mixture of 100 ml of tricresyl phosphate and 50 ml of ethyl acetate, and then 2g of laurate was added. This solution was added to 1 kg of a 10% by weight gelatin aqueous solution containing 2.5 g of dodecylbenzenesulfonic acid, stirred at high speed, and further subjected to ultrasonic stirring to obtain an emulsion. 400 g of this emulsion was added to the above photographic emulsion, a hardening agent and a spreading agent were added, and then coated on a cellulose triacetate-based support. Furthermore, a high-sensitivity photographic emulsion (see Tables 3 and 2) containing a group element compound, a black and white developing agent, and an emulsion prepared in the same manner as in Example 2 was coated on the above emulsion layer. Each of these samples was photographically processed in the same manner as in Example 2. The characteristic curve of the obtained yellow image was examined to determine the sensitivity, gamma value, and fog. Sensitivity was expressed in the same manner as in Example 1. The results are shown in Table 3.

【table】

[Table] As is clear from Table 3, it can be seen that the samples according to the present invention exhibit significantly smaller variations in photographic properties due to variations in development processing than the comparative samples. Furthermore, the gradation properties were also good. Example 6 The control emulsion used in Example 3 was coated on the control sample obtained in Example 4, and a yellow filter layer was further provided.
Twelve types of multilayer samples were prepared by coating the various emulsions used in . Each of these samples was exposed to white light and processed as in Example 2. The characteristic curves of the obtained cyan, magenta, and yellow images were examined, and the sensitivity, gamma value, and fog were determined. The results were the same as in Example 2 for all color images, and it was found that fluctuations in photographic characteristics due to fluctuations in development processing were extremely small, and at the same time, gradation was good.

Claims (1)

[Claims] 1 A water-soluble compound consisting of an element in a group of the periodic table of elements and having a molecular weight of 100 or more
A silver halide photographic material containing at least 40 mg per gram of silver, and further containing 1.2 to 120 mg of a black and white silver halide developing agent per 100 g of silver.