JPS6138461B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material containing a developer substance and having improved storage stability. It is known to incorporate developer materials into photographic elements consisting of at least one silver halide emulsion layer. This method is particularly useful for silver complex diffusion transfer materials;
-27568, 1972-28825, 1974-27435, 1973
Numerous patents and documents such as JP-A No. 47-30856, JP-A No. 51-43778, JP-A No. 46-3332, JP-A No. 49-1223 can be referred to. Further, the above method is also used in the stabilization treatment materials described in, for example, Japanese Patent Publications No. 42-702, No. 18670 of No. 44, No. 31307 of No. 44, and No. 27427 of No. 1973. Furthermore, it is also known to add a relatively small amount of developer material for the purpose of improving development progress and preventing fog. The developer solution for developing the materials for diffusion transfer and stabilization processing described above usually does not contain any developer material.
Alternatively, an alkaline activation liquid substantially free of the alkali activation liquid is used. One advantage of alkaline activating fluids is that they avoid the disadvantage of deterioration of the developer due to air oxidation in conventional highly alkaline developers containing developer materials. However, even if a developer is added to a silver halide emulsion layer or a non-light-sensitive layer such as a protective layer, an interlayer, or a subbing layer, air oxidation of the developer material cannot be avoided, and as a result, the development Undesirable effects such as decreased speed, decreased sensitivity, decreased silver image density, and fogging occur. Significant expiration of the developer may result in no image. Expiration of the developer in photographic materials to which a small amount of developer has been added for the purpose of improving development speed, as described above, not only means that the purpose cannot be achieved;
It may also cause collateral damage. Antioxidants, such as sulfite, usually sodium sulfite, are widely used to prevent atmospheric oxidation of developer materials. However, since this has the effect of dissolving silver halide, it has the disadvantage that areas that should not be developed are also developed. In addition, many of the other antioxidants have some kind of drawback or do not exhibit sufficient effects. An object of the present invention is to improve the storage stability of silver halide photographic materials containing developer substances. Another object of the present invention is to provide silver halide photographic products containing developer materials that have improved storage stability without any adverse effect on photographic properties. The present inventors have proposed a photographic material having at least a silver halide emulsion layer on a support and containing a developer substance in the emulsion layer and at least one of the non-photosensitive layers, on the other side of the support. It has been surprisingly found that the above object can be completely achieved by further containing developer material in the layer, ie the back layer. The present invention will be explained in more detail below. In the photographic material of the present invention, the developer substances contained in the silver halide emulsion layer or the non-photosensitive layer include the compounds described in the above-mentioned patent specifications. For example, polyhydroxybenzene compounds include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, tolu-hydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2.
3-dibromohydroquinone, 1,4-dihydroxy-2-acetophenone-2,5-dimethylhydroquinone, catechol, 4-phenylcatechol, 4-phenethylcatechol, 4-phenopropylcatechol, 4-t-butylcatechol ,
4-n-butylpyrogallol, 4,5-dipromocatechol, 2,5-diethylhydroquinone,
2,5-di-p-phenethylhydroquinone,
2,5-dibenzoylaminohydroquinone,
2,5-diphenyl-3,6-dibenzylhydroquinone, 2,5-diacetaminohydroquinone, etc., 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl as a 3-pyrazolidone compound -4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3
-pyrazolidone, 1-p-chlorophenyl-3-
Pyrazolidone, 1-p-methoxyphenyl-3-
Pyrazolidone, 1-phenyl-2-acetyl-3
-pyrazolidone, 1-phenyl-5,5-dimethyl-3-pyrazolidone, 1-0-chlorophenyl-4-methyl-4-ethyl-3-pyrazolidone,
1-m-acetamidophenyl-4,4-diethyl-3-pyrazolidone, 1,5-diphenyl-3-
Examples of aminophenol compounds include pyrazolidone, 1-(m-tolyl)-5-phenyl-3-pyrazolidone, and aminonaphthol compounds such as N-methyl-p-aminophenol X-sulfonic acid. Hydroquinone is preferred. , hydroquinone derivatives, and 3-pyrazolidone compounds are used. The amount of developer material used in the emulsion layer or non-photosensitive layer varies depending on the application and other factors, but ranges from about 10 milligrams/m ² for hydroquinones.
About 5 grams/m ² , and 3-pyrazolidones in the range of about 1 milligram/m ² to about 1 gram/m ² . In materials for diffusion transfer and stabilization treatment, 0.3 to 5 g/ ^m2 of hydroquinones, 0.05 to
It is common to use 1 g/m ² of 3-pyrazolidones, with the amount of silver in the emulsion layer being from 0.5 to 5 g/m ² of silver halide as silver nitrate. Typical ranges for the amount of silver may be outside the above amount ranges. These developer substances include water, preferably water-miscible organic solvents such as methanol, ethanol,
It can be introduced by a known method of dissolving it in propanol, acetone, dimethylformamide, etc. and adding it to a gelatin silver halide emulsion or a non-photosensitive layer coating solution. Supports that can be used in the photographic material of the present invention include:
Polyolefins such as polyethylene, polypropylene, and polystyrene, cellulose ester films such as cellulose acetate and cellulose nitrate, polyester films such as polyethylene terephthalate, paper, synthetic paper, or composites of these, such as paper or film with polyolefin on both or one side. Any known support can be used, such as those coated with. It is known that the back layer of the support is usually provided for the purpose of preventing halation, preventing curling, preventing static electricity, and preventing slippage. Therefore, the back layer of the photographic material of the present invention can be, for example, a layer coated to meet these purposes, such as dyes and pigments for preventing halation, antistatic agents, matting agents for preventing slippage, etc. may contain. (For example, see JP-A No. 50-99529, Japanese Utility Model Publication No. 51-42401, etc.) Regarding the type and amount of the developer substance contained in the back layer, those already described for the emulsion layer or the non-photosensitive layer are used here. Can be quoted. Compared to the developer substance on the emulsion layer side, the type and amount thereof may be the same or different. Moreover, two or more types can also be used together. Particularly preferred developer substances in the back layer are hydroquinones, preferably in loadings of 0.1 to 3 g/m ² . The photographic light-sensitive material of the present invention can be said to be a photographic product packaged on one side. That is, generally, a coated and dried silver halide photographic material is wound up into a roll as it is. Roll-shaped products are cut into narrow widths, and sheet-shaped products are cut into various sizes and packaged. Whether in the form of a roll or a sheet, the photosensitive surface and back surface of the photosensitive material are in contact with each other. When the silver halide photographic light-sensitive material of the present invention is stored in such a state for a long period of time, the developer substance contained in the emulsion layer continues to exist without undergoing any or almost no air oxidation. It was completely unexpected. Examples of silver halide photographic materials useful in the practice of the present invention include silver halide black and white photographic materials, silver halide color photographic materials, photographic materials for printing plate making, X-ray photographic materials, microphotographic materials, Examples include, but are not limited to, photosensitive materials for copying. The effects of the present invention depend on the properties of the silver halide emulsion, such as the composition of silver halide (for example, silver iodobromide, silver bromide, silver chlorobromide, silver chloroiodobromide, etc.), the crystal form of silver halide, It appears regardless of crystal habit, silver ion concentration in the emulsion, pH in the emulsion, type and amount of hydrophilic binder, etc. The production, dispersion, and physical ripening of silver halide used in the practice of the present invention can be carried out using various known methods and conditions. For example, forward mixing method, back mixing method, simultaneous mixing method, Japanese Patent Publication No. 46-7772, conversion silver halide method such as U.S. Patent No. 2592250, ammonia method, acidic or neutral method, alkaline method, U.S. Patent No. 2448534 The ethylenediamine method described in No.
The silver iodide nuclear method described in JP-A-48-65925 and various combinations thereof are advantageously used. In addition, various additives such as zinc ions, rhodium ions, iridium ions, lead ions, thallium ions, lithium ions, calcium ions, etc. are contained in the silver halide emulsion (usually added during physical ripening). One type or combination of metal ions, The Journal of Photographic Science (The
journal of Photographic Science) Vol.13, 1965
Alkylpyridinium salts, thiourea, 3-mercapto-4-methyl-5 as described in
Various crystal habit modifiers such as -ethyl-1,2,4-triazole, 1-phenyl-5-mercapto-tetrazole, and 2-mercapto-penzimidazole can be included. Furthermore, the silver halide emulsion can be chemically sensitized with various sensitizers. For example, sulfur sensitizers (e.g. hypo, thiourea, gelatin containing labile sulfur, etc.), noble metal sensitizers (e.g. gold chloride, gold rhodan, ammonium chloroplatinate, silver nitrate, silver chloride, palladium salts, rhodium salts, iridium salt,
ruthenium salts, etc.), polyalkylene polyamine compounds described in US Pat. No. 2,518,698, imino-amino-methanesulfinic acid described in German Patent No. 1,020,864, reduction sensitizers (e.g., stannous chloride, etc.) are advantageous. used for. Hydrophilic binders advantageously used to prepare a light-sensitive emulsion in the silver halide photographic light-sensitive material of the present invention include lime-treated gelatin, acid-treated gelatin, and gelatin derivatives (for example, Japanese Patent Publication No. 38-4854
No., No. 39-5514, No. 12237-12237, No. 42
−26845, U.S. Patent No. 2525753, U.S. Patent No. 2594293
No. 2614928, No. 2763639, No.
3118766, 3132945, 3186846, 3312553, British Patent No. 861414, British Patent No. 1033189
(gelatin derivatives described in the issue, etc.), albumin,
Proteins such as casein, cellulose compounds such as carboxymethylcellulose and hydroxyethylcellulose, agar, natural polymers such as sodium alginate, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives thereof, partially hydrated There are synthetic hydrophilic binders such as decomposition products,
These hydrophilic binders can be used alone or in combination. These hydrophilic binders can also be used in constituent layers of photographic materials that do not contain silver halide, such as antihalation layers.
It is also advantageously used to create intermediate layers, protective layers etc. and back layers according to the invention. Silver halide emulsions can also be spectrally sensitized in blue, green, and red. It can be a merocyanine, cyanine dye or other sensitizing dye. The constituent elements of the silver halide photographic material of the present invention may further contain various additives. For example, hardeners such as formalin, mucochlor vinegar, chromium alum, vinyl sulfone compounds, epoxy compounds, and ethyleneimine compounds, antifoggants or stabilizers such as mercapto compounds, and tetraazaindene, and saponins and alkylbenzene sulfones as surfactants. Patent Publication No. 34-7127, such as sodium acid salts, sulfosuccinic acid ester salts, anionic compounds such as alkylaryl sulfonates as described in US Pat. No. 2,600,831, and amphoteric compounds as described in US Pat. No. 3,133,816.
Fluorescent brighteners such as No. 1, waxes, wetting agents such as glycerides of higher fatty acids or higher alcohol esters, N-guanyl hydrazone compounds, 4
onium compounds, mordants such as tertiary amine compounds, diacetylcellulose, styrene-perfluoroalkylene sodium maleate copolymers, alkali salts of the reaction products of styrene-maleic anhydride copolymers and p-aminobenzenesulfonic acid. Antistatic agents such as, polymethacrylate esters,
Matting agents such as polystyrene, colloidal silicon oxide, acrylic acid esters, film property improvers such as various latexes, glycerin, gelatin plasticizers such as those disclosed in Japanese Patent Publication No. 4939-1983, styrene-maleic acid copolymers Thickeners such as No. 21574, antioxidants, PH regulators, etc. can be used. The present invention is applicable to, for example, Japanese Patent Publication No. 48-16725,
It can also be applied to lithographic printing plates applying the diffusion transfer method described in JP-A No. 30562, JP-A No. 53-21602, and the like. The processing liquid used in the diffusion transfer method contains an alkaline substance such as sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, etc., a silver halide solvent such as sodium thiosulfate, ammonium thiothianate, a cyclic imide compound, Preservatives such as thiosalicylic acid, such as sodium sulfite, thickening agents such as hydroxyethyl cellulose, carboxymethyl cellulose, antifoggants such as potassium bromide, 1-phenyl-5-mercaptotetrazole, etc., and if necessary, a developer, For example, hydroquinone, 1-phenyl-3-pyrazolidone, etc., developer modifiers, such as polyoxyalkylene compounds, onium compounds, alkanolamines, etc. can be included. The silver halide photographic material of the present invention, which is developed with a processing solution other than an alkaline activating solution, is characterized by its type,
Depending on the application, for example, ``Photographic materials and handling methods'' (Kyoritsu Shuppan, written by Goro Miyamoto, Photo Techniques Structure 2), ``Photography Technique Manual [Part 1], [Part 2]'' (Photo Kogyo Special Issue, Photo Kogyo Publishing) Processes such as exposure, development, stopping, fixing, bleaching, and stabilization that are known in the art can be performed, such as those described in J.D. Next, Examples will be described to further specifically explain the present invention, but the present invention is not limited thereto, and various applications can be made within the scope of the claims. Example 1 In accordance with Japanese Utility Model Publication No. 51-42401, the back side of a 135 g/m ² double-sided polyethylene coated paper was treated with a corona discharge, and then the following pack layer was applied at a rate of 50 g/m ² (moisture). Gelatin 25g Thyroid 308 (product name of silica manufactured by Fuji Davison) 5g Saponin (12% aqueous solution) 10ml Formalin (12% aqueous solution) 3ml Add water to make a total volume of 500g Furthermore, after corona discharge treatment on the other side of the coated paper, A layer of anti-halation gelatin containing carbon black is provided on which a layer of gelatin with an average particle size of 5.
An ortho-sensitized silver chlorobromide emulsion (20 mole % silver bromide) containing μ silica particles (Syroid 308 above) was coated at 2.0 g/m ² as silver nitrate. The antihalation layer and emulsion layer contain formalin as a hardening agent. After drying, the emulsion layer was heated at 40°C for 3 days, and the above-mentioned JP-A-53-100 was applied on top of this emulsion layer.
Polymer No. 5 described in 21602 (imidazole group 5
A lithographic plate using a diffusion transfer method by applying a palladium sulfide core solution containing 1.0 g/m ² of hydroquinone and 0.5 g/m ² of 1-phenyl-3-pyrazolidone (vinyl polymer containing 95 mol % of amide groups) A printing plate (comparative sample) was prepared. Hydroquinone was added to the back layer of the comparative sample above.
Two types of samples of the present invention were prepared in the same manner except that they were added at a rate of 0.5 g/m ² and 1.0 g/m ² . After cutting these samples, 20 pieces of the same sample were stacked in the same direction and sealed in a black plastic bag, and each bag was heated at 50℃ and 80℃.
It was stored at %RH for 5 days. After sensitometric exposure of each sample immediately after production and after storage as described above, the sample was heated to 30°C using the following processing solution.
Developed for 30 seconds and stopped with neutralizing solution. Developer solution Water 750ml Sodium hydroxide 20g Anhydrous sodium sulfite 50g Sodium thiosulfate (5H ₂ O) 10g Make the total volume 1 with water Neutralizing solution Water Citric acid Sodium citrate Colloidal silica (20% solution) Ethylene glycol Add the total volume to 1 with water 1. The comparison sample showed significant desensitization, softening of tone, and significant decrease in the amount of transferred silver upon storage, but the samples of the present invention showed no change in photographic properties even after storage, except for those not in contact with the back layer. It wasn't recognized. This result was obtained by rolling these samples into a roll and heating them at 35°C and 83°C.
The results were similar to those obtained after storage for 2 months at %RH. Example 2 A 110 g/m ² paper support coated on both sides with polyethylene was coated with carbon black and 1 g/m ² of hydroquinone as an antihalation agent on one side.
A 3 g/m ² undercoat layer of gelatin containing 0.3 g/m ² of 1-phenyl-4-methyl-3-pyrazolidone was provided, and on top of this, silver chloride with an average particle size of 0.3 μ was coated with 1.5 g/m 2 of silver chloride in terms of silver nitrate. A gelatin silver halide emulsion layer (gelatin 1 g/m ^{2 )} was orthosensitized and further contained 0.2 g/m ² of hydroquinone. A gelatin layer of 3 g/m ² was provided on the back side of the paper support for the purpose of preventing curling (comparative sample). Samples A to E of the present invention were similarly prepared by incorporating the following developer substances into the back layer of the comparative sample.

[Table] After each sample was stored in the same manner as in Example 1, it was exposed to light for sensitometry, brought into close contact with a positive material, passed through a normal developing machine containing the following diffusion transfer processing solution, and peeled off after 30 seconds. did. Water 800ml Anhydrous sodium sulfite 40g Sodium phosphate (12H ₂ O) 75g Potassium hydroxide 5g Sodium thiosulfate (5H ₂ O) 20g Potassium bromide 1g 1-phenyl-5-mercapto tetrazole 0.1g Make the total volume 1 with water. The comparison sample showed greater desensitization and lower contrast after storage than the sample immediately after production, and the silver concentration obtained on the positive material was also significantly lower. The samples of the present invention showed almost no change in photographic properties even after storage, and samples A and B were particularly good.

Claims (1)

[Claims] 1. A photographic material having at least a silver halide emulsion layer on a support and containing a developer substance in the emulsion layer and at least one non-photosensitive layer on the side of the emulsion layer with respect to the support. A silver halide photographic material comprising a layer containing a developer substance on the other side of the body.