JPS6146818B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver complex diffusion transfer method, and particularly to a photographic material used therefor. The principle of silver complex diffusion transfer method (hereinafter referred to as DTR method) is described in US Pat. No. 2,352,014 and is well known. In the DTR process, silver complex salts are imagewise transferred by diffusion from a silver halide emulsion layer to an image-receiving layer, and they are converted into a silver image, often in the presence of physical development nuclei. For this purpose, an imagewise exposed silver halide emulsion layer is placed in contact with, or brought into contact with, an image-receiving layer in the presence of a developing agent and a silver halide complexing agent, and the unexposed Exchange the silver halide with a soluble silver complex. In the exposed parts of the silver halide emulsion layer, the silver halide is developed to silver (chemical development);
Therefore, it cannot be dissolved further and therefore cannot be diffused. In the unexposed portions of the silver halide emulsion layer, the silver halide is converted to soluble silver complex salts, which are transferred to the image-receiving layer where they form a silver image, usually in the presence of development nuclei. In a direct positive silver halide emulsion, the effects of silver halide in exposed and unexposed areas are reversed. It is well known that in order to produce a transferred silver image of high contrast and sharpness in the image-receiving layer, the transfer silver must be formed rapidly. This is done by rapid development of the transferred silver complex, for example silver thiosulphate, so that this complex is no longer able to diffuse laterally into the nucleus-containing image-receiving layer. Typical processing solutions used in the DTR process include silver halide complexing agents such as thiosulfates, alkalinities such as sodium hydroxide, preservatives such as sulfites, and developing agents such as hydroquinone and 1-phenyl-3-pyrazolidone. Consists of at least the main drug. However, in a highly alkaline processing solution containing this developing agent, the developing agent has the disadvantage that it is subject to air oxidation and loses its effectiveness. It is known that this drawback can be largely avoided by incorporating it into a hydrophilic colloid layer that has water permeability. In diffusion transfer materials containing such a developing agent, an alkaline active liquid containing no or substantially no developing agent is usually used. The DTR method using an alkaline activation solution was developed by Tokko Sho.
Reference may be made to specifications such as No. 39-27568, No. 47-30856, No. 43778 No. 51-Sho. According to these patent specifications, the amount of dihydroxybenzene compound and 3-pyrazolidone compound used as developing agents is 50 mg, particularly 100 mg or more and up to 5 g per square meter of the photosensitive material. However, even when a developing agent is introduced into the material, air oxidation of the developing agent cannot be completely avoided, which not only causes a decrease in development speed and contrast, but also causes fogging. It has its drawbacks. Some of these drawbacks are due to the direct introduction of the developing agent into the DTR material, while others are also due to the high loading of the developing agent. It is the developing agent
The amount normally contained when introduced into DTR materials is compared to the amount normally contained in DTR processing liquid.
Approximately 5 times the amount of silver halide is used per unit of silver halide, which requires special attention to the inefficient use of the developing agent, the limits of the developing agent content, and the negative effects of excess agent. Teach the need. However, the use of less than about 50 mg of developing agent, especially 3-pyrazolidone, per square meter results in inefficient use and increases the dependence on the processing temperature of the DTR processing solution, for example, 10 to 15°C.
Processing at low temperatures, such as in the above, results in a disadvantage of reduced contrast. This decrease in contrast sometimes causes the silver image formed on the image-receiving layer to
Despite the use of a blackening agent such as phenyl-5-mercaptotetrazole, the silver image was yellowish in color. There is a need for a silver complex diffusion transfer method capable of producing transferred silver images of high contrast and high sharpness and free from the above-mentioned drawbacks, and it is an object of the present invention to provide a diffusion transfer material for an alkaline activating solution particularly suitable for this method. is the object of the present invention. In the present invention, at least one dihydroxybenzene compound and two or more 1-phenyl-3 - pyrazolidone compound, and the 3-pyrazolidone compound was found to be a combination of a compound having a substituent at at least the 4-position and a compound having no substituent. In a preferred embodiment of the present invention, 0.3 to 3.0 g/m ²
The total amount of dihydroxybenzene and 3-pyrazolidone is 0.1 g/m ² or more, and
A diffusion transfer material is provided in which the amount of 1-phenyl-4-unsubstituted-3-pyrazoline to 4-substituted-3-pyrazolidone is less than 1/3 by weight. According to a preferred embodiment of the invention, a silver halide emulsion layer containing 0.5 to 3.5 g/m ² of silver halide, converted to silver nitrate, and a dihydroxyl, such as hydroquinone, containing 0.3 to 3.0 g/m ² of silver halide, Benzene compounds and 0.08-0.8 g/m ² of 1-phenyl-4
- A diffusion transfer material is provided in which a substituted-3-pyrazolidone is combined with 1-phenyl-4-unsubstituted-3-pyrazolidone in an amount of 0.005 to 0.05 g/m ² less than 1/3 of its weight. be done. According to another preferred embodiment of the present invention, in a diffusion transfer material having an antihalation layer containing carbon black on a support, and a silver halide emulsion layer provided thereon, the antihalation layer is provided with a silver halide emulsion layer.
0.3-3.0 g/m ² of dihydroxybenzene compounds such as hydroquinone and 0.08-0.8 g/m ² of 1-phenyl-4-hydroxyalkyl group substitution.
A diffusion transfer material containing 3-pyrazolidone and 0.005 to 0.05 g/m ² of 1-phenyl-3-pyrazolidone, which is less than 1/3 of the weight of 3-pyrazolidone, is provided. This was found to be preferable for achieving the object of the present invention without increasing the fog caused by carbon black as known from Japanese Patent Application Laid-Open No. 50-68520. Representative examples of dihydroxybenzene compounds used in the present invention are as follows. A-1 Hydroquinone A-2 Chlorohydroquinone A-3 Methylhydroquinone A-4 2,5-dimethylhydroquinone 1-Phenyl-4-substituted- used in the present invention
Representative examples of 3-pyrazolidone compounds include the following. B-1 1-phenyl-4-methyl-3-pyrazolidone B-2 1-phenyl-4,4-dimethyl-3-
Pyrazolidone B-3 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone B-4 1-P-chlorophenyl-4-methyl-
4-hydroxy-3-pyrazolidone B-5 1-phenyl-4-hydroxymethyl-
3-Pyrazolidone B-6 1-(P-tolyl)-4,4-dihydroxymethyl-3-pyrazolidone Representative examples of the 1-phenyl-4-unsubstituted-3-pyrazolidone compound used in the present invention are as follows. Can be mentioned. C-1 1-phenyl-3-pyrazolidone C-2 1-(m-tolyl)-3-pyrazolidone C-3 1-phenyl-2-acetyl-3-pyrazolidone These developing agents are used in the silver halide emulsion layer, It is added to at least one layer such as a subbing layer, a protective layer (or release layer), an interlayer, etc., which may be the same layer or a separate layer. In order to obtain a transferred silver image with high contrast and high sharpness, it is preferable that the amount of gelatin binder in the silver halide emulsion layer is as small as possible. As mentioned above, the introduction of a large amount of a developing agent tends to cause various disadvantages (e.g. agglomeration), and therefore it is preferable to contain a substantially effective amount of the developing agent in a relatively binder-rich layer such as an antihalation layer. It is desirable to do so. Best results are obtained when the antihalation layer containing carbon black has a pH of 4.5 or less. Preferably, the silver halide emulsion layer also has a pH of 5.0 or less. Carbon black can be used in amounts ranging from about 0.01 to 2.0 g/m ² , although other amounts may be used. Carbon black can be used dispersed with various surfactants. The surfactant used is preferably one that does not adversely affect photography, and any surfactant known to be used in coating solutions for photographic layers can be used. Examples include anionic surfactants such as higher alcohol sulfate salts, higher alkylaryl sulfonates, higher alkylnaphthalene sulfonates, higher alkyl phosphates, and dialkyl sulfosuccinates. 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 side of the support is usually provided for purposes such as anti-halation, anti-curl, anti-static, anti-slip, etc., if necessary. Therefore, the back side 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, mattifying agents for preventing slippage, etc. may contain. It is desirable that the pH of the back layer be 5 or less, preferably 4.5 or less. The silver halide emulsions used in the present invention include silver chloride, silver bromide, silver chlorobromide, and those containing silver iodide. The silver halide crystal habit, grain size, grain size distribution, etc. can be arbitrary. The method for producing the silver halide emulsion may also be any known method. Furthermore, the silver halide emulsion can be chemically sensitized with various sensitizers. For example, sulfur sensitizers (e.g. hybo, 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,
rutinium salts, etc.), polyalkylene polyamine compounds described in U.S. Patent No. 2,518,698, iminoamino-methanesulfinic acid described in German Patent No. 1,020,864, reduction sensitizers (e.g., stannous chloride, etc.), etc. are advantageously used. used. Hydrophilic binders that are 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
-26345, U.S. Patent No. 2525753, U.S. Patent No. 2594293
No. 2614928, No. 2763639, No. 2763639, 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 are also advantageously used to create non-photosensitive layers such as antihalation layers, intermediate layers, protective layers (or release layers) or image-receiving layers or even back layers, including carbon black. . The binder of the silver halide emulsion layer is preferably at most 2 parts by weight, preferably up to 1.0 parts by weight, based on the silver halide calculated as silver nitrate, and is provided between the silver halide emulsion layer and the support. More preferable results can be obtained by using a larger amount of the binder in the carbon black layer than the binder in the emulsion layer, preferably 2 parts by weight or more. 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, formalin, mucochloric acid, chromium alum, vinyl sulfone compounds, epoxy compounds,
Hardeners such as ethyleneimine compounds, merkabut compounds, antifoggants or stabilizers such as tetraazaindene, surfactants such as sabonin, sodium alkylbenzene sulfonate, sulfosuccinic acid ester salts, and alkylaryls described in U.S. Pat. No. 2,600,831. In addition, anionic compounds such as sulfonates and amphoteric compounds as described in US Pat. Wetting agents such as N-guanyl hydrazone compounds, quaternary onium compounds, mordants such as tertiary amine compounds, diacetyl cellulose, styrene-perfluoroalkylene sodium maleate copolymers, styrene-maleic anhydride copolymers and P. -Antistatic agents such as alkali salts of reactants with aminobenzenesulfonic acid, matting agents such as polymethacrylic esters, polystyrene, colloidal silicon oxide, acrylic esters, film property improvers such as various latexes, glycerin, Gelatin plasticizers such as those disclosed in Japanese Patent Publication No. 43-4939, styrene-maleic acid copolymers, thickeners such as those disclosed in Japanese Patent Publication No. 36-21574, antioxidants, PH regulators, etc. can be used. The back layer may further contain the developer materials described above. For example, the present invention is applicable to
It can also be applied to lithographic printing plates applying the diffusion transfer method described in 30562, 1972-21602, etc. 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 hydroxyethylcellulose, carboxymethylcellulose, antifoggants such as potassium bromide, 1-phenyl-5-mercaptotetrazole, etc., developer modifiers such as polyester, etc. It can include oxyalkylene compounds, onium compounds, alkanolamines, and the like. Next, Examples will be described to further specifically explain the present invention, but the present invention is not limited to these examples, and various applications can be made within the scope of the claims. Example 1 One side of a 110 g/ ^m2 paper support coated on both sides with polyethylene was coated with 0.3
An undercoat layer of 3 g/m ² of gelatin containing 1 g/m ² of carbon black and 1 g/m 2 of hydroquinone was applied, and on top of this a 3 g/m ² undercoat layer of gelatin containing 0.3 μm average particle size of silver chloride, converted to silver nitrate, of 1.5 g/m 2 of carbon black and 1 g/m 2 of hydroquinone. A gelatin silver halide emulsion layer (gelatin 1 g/m ² ) is orthosensitized and further contains 0.2 g/m ² of hydroquinone ^. Both the undercoat layer and emulsion layer are adjusted to pH 4.1 and hardened with formalin. A gelatin layer of 4 g/m ² is provided on the back side of the support, and a sample is prepared in which the pH of the gelatin layer is 4.5. (Sample 1). Samples 2 to 2 were prepared in the same manner except that the undercoat layer of Sample 1 contained 1-phenyl-3-pyrazolidone as shown in the table below.

[Table] After sensitometric exposure, these samples were brought into close contact with a positive material, passed through a conventional developer containing the following diffusion transfer developer, and peeled off after 60 seconds. 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
0.1 g The total amount was made up to 1 with water. Processing was carried out by changing the temperature of the developing solution to 10°C, 20°C, 30°C and 40°C. Samples 1 to 9 and 13 had some drawbacks, such as a marked decrease in contrast, a yellowish-brown silver image, and a decrease in maximum density during low-temperature or high-temperature processing. Samples 10 to 12 of the present invention have extremely high contrast against temperature changes of 10 to 40°C, the changes are extremely small, and are black silver images with high sharpness.
The maximum concentration was also high. Moreover, the samples of the present invention had extremely stable storage stability even when left for a long time under high temperature and high humidity. Example 2 Example 1 was repeated. However, replacing hydroquinone with methylhydroquinone, 1-phenyl-3
- Pyrazolidone was changed as follows.

[Table] Invention samples 14 and 16, comparative samples 15, 17 and
It was confirmed that the results of 18 were the same as in Example 1.

Claims (1)

[Claims] 1. A silver complex salt diffusion transfer material containing a silver halide developing agent in a silver halide emulsion layer provided on a support and/or a hydrophilic colloid layer in a water-permeable relationship therewith, in which a dihydroxybenzene compound is used as the developing agent. and two or more 1-phenyl-3-pyrazolidone compounds in a total amount of 0.1 g/m ² or more, wherein the 3-pyrazolidone compound is 1-phenyl-4-substituted-3-
An improved diffusion transfer material comprising at least a combination of pyrazolidone and 1-phenyl-4-unsubstituted-3-pyrazolidone in an amount of 1/3 or less of its weight.