JPH0473866B2 - - Google Patents

Description

[Detailed description of the invention]

(A) Industrial Application Field The present invention relates to a processing method using a silver complex diffusion transfer processing solution, particularly a running processing method. (B) Prior art and its problems The principle of the silver complex diffusion transfer method (hereinafter referred to as the DTR method) is described in the specification of U.S. Patent No. 2,352,014, and there are many other patents and documents. Are known. In other words, under the DTR method,
The silver complex salts are imagewise transferred by diffusion from the silver halide emulsion layer to the image-receiving layer, and they are converted into a silver image, often in the presence of processing 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 solvent, and the unexposed halide emulsion layer is Converts silver into soluble silver complexes. In the exposed portions of the silver halide emulsion layer, the silver halide is developed to silver so that it cannot be further dissolved and therefore cannot be diffused. In the unexposed areas of the silver halide emulsion layer, the silver halide is converted to a soluble silver complex salt,
They are transferred to the image receiving layer where they form a silver image, usually in the presence of development nuclei. The DTR method is used for document reproduction, lithographic printing plate production,
A wide range of applications are possible, including the production of block printing materials and instant photography. In particular, when reproducing documents or preparing printing materials, a negative material having a silver halide emulsion layer and a positive material having an image-receiving layer containing physical development nuclei are used.
Usually, they are brought into close contact in a DTR processing solution containing a silver complex forming agent to form a silver image on the image-receiving layer of a positive material. The silver image must be pure black or black with a bluish tinge, and must also have a sufficiently high density. Furthermore, it is important to have high contrast and sharpness and good image reproducibility, and it is desirable that the transfer speed is high. Moreover, it is necessary that the good quality of the positive material does not depend greatly on the processing conditions (e.g. time, temperature), or that the quality does not deteriorate due to running processing (continuing to use the processing solution for a long period of time). . Based on the principle of the DTR method described above, it can be easily inferred that the image forming process will be greatly affected by processing conditions, especially processing temperature, processing speed, etc. It is also well known. General specific examples of characteristic changes caused by changes in the processing environment in the DTR method, especially changes in processing temperature and changes in conveyance conditions, are as follows: (1) Sensitivity, tone, color tone, density (reflection density, (2) Low-temperature processing tends to cause contamination (due to the formation of fine silver colloid) on the image-receiving sheet. (3) The ability to form minute images, such as fine lines or minute dots, is affected by the processing temperature. For example, it decreases as the conveyance speed increases or as the conveyance speed decreases. To date, as a means to solve the above-mentioned problems, for example, Japanese Patent Application Publications No. 48-93338, No. 55-79445, No. 55-157738, No. 176-176036, No. 58-72143 have been used.
Although many processing solutions have been proposed, the reason why they have not been an overall satisfactory method is that the DTR method has a delicate balance between chemical development, dissolution, diffusion, and physical development. This is probably because it was thought to be difficult to control because it was based on Moreover, the above-mentioned characteristic changes become noticeable due to running processing, and may even occur again. In general, image forming systems using the DTR method are
A very simple process is used. For example, the processor includes a tray for holding a transfer developer, a squeeze roller for bringing a negative sheet and a positive sheet into close contact with each other, and a motor for rotating the squeeze roller. If such a processor performs running processing using approximately one processing solution, there are limits to the processing capacity (amount that can be processed) of the sheet material and the life span (period that it can be processed) of the processing solution, and there are limits to the processing of unprocessed materials. It took several days at most to leave the solution (that is, the new solution) alone. Therefore, in reality, the exhausted processing solution is replaced with a new solution, or, if running processing is to be continued, the new solution or a concentrated solution of the new solution is replenished. In general, the following factors can be considered as factors that cause various properties to change when a DTR treatment liquid is subjected to running treatment. That is, processing agents that play a major role in DTR development, such as silver halide solvents such as thiosulfate, preservatives such as sulfite, and alkaline agents such as sodium hydroxide and sodium phosphate, are reduced and compositionally changed due to consumption; Processing agents become concentrated due to evaporation of water from the processor, PH decreases due to the absorption of carbon dioxide gas in the air, and if a developing agent is included, its oxidation. It is thought that the processing characteristics are changing. Concentration of the processing agent due to water evaporation can be significantly improved by lowering the concentration of the processing agent, especially inorganic salts, in the new processing solution, or by using a processor as shown in Utility Model Application No. 58-65045. can do.
However, a decrease in pH due to absorption of carbon dioxide gas in the air is an unavoidable problem, and is a factor that greatly controls running processability. Therefore, in the conventional method of replenishing new liquid or concentrated liquid of new liquid, it has not been possible to extend the running processing period very much. Against this background, the present inventor continued research to improve running properties, and as a result, discovered a processing method that can ensure running properties for a much longer period of time than conventional running lifespans. (C) Object of the Invention An object of the present invention is to provide a processing method that dramatically improves the running properties of a processing solution for silver complex diffusion transfer. Another object of the present invention is to provide a processing method using a processing liquid for silver complex diffusion transfer, which has dramatically improved running processability and can obtain good transfer characteristics with little dependence on changes in processing conditions. It is in. (D) Structure of the Invention The above-mentioned object of the present invention is to provide a running treatment method using a processing solution for silver complex diffusion transfer and a replenisher having an inorganic salt concentration not lower than the inorganic salt concentration of the processing solution. The processing solution contains at least an amino alcohol having a pKa value of less than 9 in an aqueous solution (25°C) containing 50% by weight of ethanol, and the replenisher contains the above-mentioned
This was achieved by a treatment method characterized by containing at least an amino alcohol having a pKa value of 9 or more. The present invention will be explained in more detail below. According to the typical treatment method of the present invention, the above
A processing method is disclosed that uses a processing solution containing a combination of an amino alcohol with a pKa value of less than 9 and an amino alcohol with a pKa value of 9 or more, and a replenisher having substantially the same formulation as the processing solution. The pKa value of amino alcohol is, for example, “STABILITY CONSTANTS OF METAL−
ION COMPLEXES” (Special Publication No.
17 (1964) and No. 25 (1971), THE
(published by CHEMICAL SOCIETY, LONDON), “Basic Chemical Handbook” (Revised 3rd edition, June 25, 1982)
published by Nippon Maruzen Co., Ltd.), etc.
It can also be easily measured. The pKa value in the present invention is defined as one measured at 25° C. in a mixed solvent of ethanol and water at a weight ratio of 50:50. However, in this specification, the pKa value in an aqueous solution of amino alcohol may be expressed as pKa [water]. The value of pKa [water] is generally slightly higher (about 0.2) than the pKa value of the above mixed solvent, and for example, the following relationship exists.

[Table] Furthermore, the pKa [water] of amino alcohol is generally
Indicates a higher value. The present inventors have determined that the amino alcohols with a pKa value of less than 9 and the amino alcohols with a pKa value of 9 or more have a pKa value of the treatment liquid that has absorbed carbon dioxide gas, that is, carbonic acid (H ₂ CO ₃ ).
It was confirmed through experiments that they showed a low pKa and a high pKa, respectively. However, while the treatment solution is relatively new, pKa9
The above activity of amino alcohol mainly works,
When the PH of the processing solution is lowered by the running process, the activity of the amino alcohol with a pKa of less than 9 acts primarily, resulting in a processing solution with excellent running processability. In addition, the pKa mentioned above
different amino alcohols can be combined to ensure sufficient alkaline capacity, thereby also allowing the use of inorganic alkaline agents, such as trisodium phosphate, to be reduced or even eliminated. Therefore,
If running processing is performed while using this processing solution as a replenisher, the running processing period can be further extended significantly. The amino alcohol having a pKa of 9 or more in the treatment liquid described above may be another alkaline agent. Furthermore, the replenisher does not necessarily need to contain amino alcohol with a pKa of less than 9. That is, the processing solution contains an amino alcohol with a pKa of less than 9 to ensure the developing ability after running,
The replenisher contains an amino alcohol with a pKa of 9 or more to restore the processing ability of the new processing solution.
Of course, as mentioned above, both the processing solution and the replenishment solution
It goes without saying that a treatment method containing an amino alcohol with a pKa of less than 9 and a pKa of 9 or more is preferred. The amino alcohol used in the present invention is a primary alcohol having at least one hydroxyalkyl group,
It is a secondary or tertiary amine compound, particularly preferably a secondary or tertiary amine. Amino alcohol includes compounds represented by general formula (A). General formula (A) (X and X' represent a hydrogen atom, a hydroxyl group, or an amino group. l and m represent an integer of 0 or 1 or more, and n represents an integer of 1 or more.) Specifically, ethanolamine, diethanolamine, triethanol Amine, diisopropanolamine, N-methylethanolamine, N-
Aminoethylethanolamine, N,N-diethylethanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine, N-
Ethyldiethanolamine, 3-aminopropanol, 1-amino-propan-2-ol, 4-
Aminobutanol, 5-amino-pentane-1-
Examples include ol, 3,3'-iminodipropanol, N-ethyl-2,2'-iminodiethanol, and the like. Furthermore, the aforementioned 2-amino-2-(hydroxymethyl)propane-1,3-diol and 2-amino-2-methylpropane-1,3-diol can also be used. Generally speaking, the pKa value defined above is that amino alcohols having one hydroxyalkyl group have pKa9.
Based on the above, it can be said that an amino alcohol having two or more hydroxyalkyl groups has a pKa of less than 9. In a preferred embodiment, the difference in pKa values of the amino alcohols combined is 0.3 or more, preferably 0.5.
The content ratio is preferably in the range of 2:8 to 8:2 as a molar ratio. The amount of amino alcohol contained in the processing solution and replenishment solution, whether used alone or in combination,
The total amount is preferably in the range of 0.2 to 2 moles per unit. Further, the amount contained in the replenisher may be equal to or greater than the amount contained in the processing liquid. The DTR treatment liquid used in the present invention should preferably contain as little inorganic salt as possible. In particular, phosphates (e.g. Na ₃ PO ₄ ), which are well known as alkaline agents for alkaline activation solutions, have traditionally been
Although it has been used in an amount of 0.15 to 0.25 mol, it is preferable that it be contained in an amount of about 0.1 mol or less or not, since it has a strong effect of suppressing swelling of the gelatin layer. Sulfites are approx.
0.2 to about 0.5 mole/thiosulfate, about 0.02 to about
A range of 0.15 mol/l is preferred, and the total amount of inorganic salts is preferably in a range of about 0.3 to about 0.7 mol/l. The amount of inorganic salts in the replenisher may be the same as that of the processing liquid, or may be greater than the content of the processing liquid if the inorganic salt concentration of the processing liquid is low as described above. The DTR treatment liquid used in the present invention further includes, for example, MOH (M is an alkali metal) 0 to 0.4 mol/,
The amount of P-dihydroxybenzene developing agent can be 0 to 0.25 mol/mol. Furthermore, if desired, thickening agents such as carboxymethyl cellulose,
Hydroxyethylcellulose, antifoggants such as potassium bromide, benzotriazole, toning agents such as 1-phenyl-5-mercabutotetrazole, development modifiers such as polyoxyalkylene compounds, quaternary ammonium salts, development nuclei such as UK It can contain various compounds used in DTR processing solutions, such as those described in Patent No. 1001558 and, if necessary, 1-phenyl-3-pyrazolidones. These various compounds can be contained in the replenisher solution either in the same composition as in the processing solution or in a different composition. The pH of the processing solution is the pH at which the developing agent is activated, usually about
10-14, preferably about 11-14. The optimum pH for a particular DTR method varies depending on the photographic element used, the desired image, the types and amounts of various compounds used in the processing liquid composition, processing conditions, etc. When carrying out the DTR method, as described in the specifications of British Patent Nos. 1000115, 1012476, 1093177, etc., a photosensitive silver halide emulsion layer and/or an image receiving layer, or It is common practice to incorporate a developing agent into another adjacent water-permeable colloid layer. Therefore, the processing solution used in the development step can be a so-called alkaline activating solution that does not contain a developing agent. A typical negative material for the DTR method is composed of at least one silver halide emulsion layer provided on a support, and the amount of silver halide, calculated as silver nitrate, is generally in the range of 0.5 g to 3.5 g/ ^m2 . applied. In addition to this silver halide emulsion layer, auxiliary layers such as an undercoat layer, an intermediate layer, a protective layer, and a release layer are provided as necessary. For example, the negative material used in the present invention is a water-permeable binder such as those described in Japanese Patent Publication No. 38-18134 and 18135, etc., such as methylcellulose, sodium salt of carboxymethylcellulose, sodium alginate, etc., which are halogenated. It can be used as a covering layer for the silver emulsion layer to ensure uniform transfer, and this layer is so thin that it does not substantially prevent or suppress diffusion. The halogenated emulsion layer in the negative material and the image receiving layer in the positive material both contain hydrophilic colloid substances such as gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose, dextrin, Contains one or more hydrophilic polymeric colloidal substances such as soluble starch, polyvinyl alcohol, and polystyrene sulfonic acid. The silver halide emulsion consists of silver halides, such as silver chloride, silver bromide, silver chlorobromide, and iodides thereof, dispersed in the above-mentioned hydrophilic colloid. Silver halide emulsions can be sensitized in a variety of ways when they are manufactured or coated. Chemically sensitized by methods well known in the art, such as with sodium thiosulfate, alkylthioureas, or with gold compounds such as gold rhodan, gold chloride, or a combination of both. Good too. The emulsions are further sensitized, usually to a range of about 530 to about 560 nm, but can also be panchromatically sensitized. Direct positive silver halide emulsions may also be used. The silver halide emulsion layer and/or the image-receiving layer may contain any compound commonly used for carrying out the silver complex diffusion transfer method. These compounds can include, for example, fog suppressants such as tetrazaindene and mercaptotetrazoles, coating aids such as saponin and polyalkylene oxides, hardeners such as formalin and chrome alum, and plasticizers. The support used for negative or positive materials is any commonly used support. They include paper, glass, films such as cellulose acetate films, polyvinyl acetate films, polystyrene films, polyethylene terephthalate films, etc., metal supports coated on both sides with paper, coated on one or both sides with α-olefin polymers, e.g. polyethylene. Paper supports can also be used. The positive material may contain physical development nuclei, such as heavy metals or their sulfides. In one or more layers of the positive material, substances which play a significant role in the formation of the diffusion transfer image, such as black toners, such as those described in British Patent No. 561,875 and Belgian Patent No. 502,525, such as -Phenyl-5-mercaptotetrazole may be included. The positive material may also contain a fixing agent such as sodium thiosulfate in an amount of about 0.1 to about 4 g/m ² . (E) Examples and Comparative Examples The present invention will be explained in more detail below using Examples, but is of course not limited to these. Example 1 On one side of a 110 g/m ² paper support coated on both sides with polyethylene, an image receiving layer consisting of gelatin containing nickel sulfide nuclei and carboxymethyl cellulose (4:1) was coated with a hydrophilic colloid to a dry weight of 3 g/m ^2. A positive material was prepared by providing the following conditions. On the other hand, on the same paper support as the positive material, carbon black and 1
A gelatin subbing layer (gelatin 3.5 g/m 2 ) containing g/m ² of hydroquinone and 0.3 g/m ² of 1-phenyl-4-methyl-3-pyrazolidone was applied, on which a gelatin subbing layer (gelatin 3.5 g/m ² ) containing 0.3 g/m 2 of hydroquinone and 0.3 g/m 2 of 1-phenyl-4-methyl-3-pyrazolidone was applied. A gelatin silver halide emulsion layer (gelatin silver halide emulsion layer) containing 1.5 g/m ² of silver chlorobromide (silver bromide 5 mol %) in terms of silver nitrate, and further containing 0.2 g/m ² of hydroquinone, etc.
1.5 g/m ² ) to prepare a negative material. The following treatment solution was prepared. Na ₂ SO ₃ 50g Na ₂ S ₂ O ₃・5H ₂ O 18g KBr 1g 1-phenyl-5-mercaptotetrazole 0.1g N-methylethanolamine 0.4 mol N-methyldiethanolamine 0.3 mol Adjust to 1 with water This treatment solution 1 A commercially available processor (for example, One Step S-Processor, Mitsubishi Paper Mills product name)
Place negative material and positive material (both A4 size)
30 sets were processed. The amount of processing solution taken out per set was approximately 3 ml. The negative material was a continuous-tone manuscript exposed through a 133-line/interface contact screen using an ordinary plate-making camera. Processing liquid temperature is 20
℃, and was peeled off after a transfer time of 60 seconds. Running treatment test Treatment solution treated as described above (remaining amount: approx. 900ml)
The processor was left open for 7 days with the lid removed. The remaining volume in each case was approximately 680 ml. Next, 320 ml of the processing solution was added as a replenisher to make the solution about 1, and 30 sets of negative and positive materials were processed again as described above, and the characteristics of the 30th set were evaluated. This operation was performed every 7 days for one month. Table 1 shows the maximum reflection density value and the quality of halftone dots.
Peelability, yellow stain and transfer unevenness are ○ (good),
The evaluation results are shown as △ (poor) and × (very poor).

[Table] The results in Table 1 show that according to the treatment method of the present invention,
This shows that long-term running processing is possible with almost no change in characteristics. The replenishment method in the present invention may be performed by a liquid level replenishment method. Comparative Example Example 1 was followed except that the treatment liquid and replenisher were of the following formulation. The results are shown in Table 2. Na ₃ PO ₄・12H ₂ O 70g Na ₂ SO ₃ 50g Na ₂ S ₂ O ₃・5H ₂ O 18g KBr 1g 1-phenyl-5-mercaptotetrazole 0.05g N-methylethanolamine 0.4g Adjust to 1 with water

[Table] Example 2 Example 1 was followed except that the following formulations were used as the processing liquid and replenisher. The results were similar to those in Example 1. Na ₃ PO ₄・12H ₂ O 35g Na ₂ SO ₃ 50g Na ₂ S ₂ O ₃・5H ₂ O 15g 1-phenyl-5-mercaptotetrazole 0.1g KI 0.1g N,N-diethylethanolamine 0.4 molDiethanolamine 0.2 mol Reethanolamine 0.2 mol Water to 1 Example 3 Example 1 was followed except that the following formulation was used as a treatment and replenisher. The results were similar to those in Example 1. Na ₂ SO ₃ 40g Na ₂ S ₂ O ₃・5H ₂ O 15g 1-phenyl-5-mercaptotetrazole 0.07g Benzotriazole 0.14g N-ethylethanolamine 0.3 mol N-ethyldiethanolamine 0.5 mol Example of adjusting to 1 with water 4 The direct positive silver halide photosensitive material described in Example 4 of JP-A-59-45441 was used as the negative material, and the gelantin image-receiving layer (3 g/m ² ) containing palladium sulfide nuclei was formed using polyester as the positive material. The one provided on the film was used. Example 1 was followed except that the following formulations were used as the processing liquid and replenisher. NaOH 5g Na ₂ SO ₃ 60g Na ₂ S ₂ O ₃・5H ₂ O 20g Hydroquinone 15g 1-phenyl-3-pyrazolidone 1.5g 1-phenyl-5-mercaptotetrazole
0.1 g KI 0.05 g N-methylethanolamine 0.5 mol N-methyldiethanolamine 0.3 mol Triethanolamine 0.2 mol At a transmission density of 3.8, which is set to 1 with water, good halftone quality characteristics could be maintained with almost no change. Example 5 In Example 4, the same replenisher was used except that N-methyldiethanolamine and triethanolamine were excluded. The results were similar. (F) Effects of the Invention According to the running treatment method of the present invention, it has become possible to perform a permanent running treatment for a significantly longer time than in the past while maintaining the good properties of the new solution.

Claims (1)

[Claims] 1 A method of running treatment using a processing solution for silver complex diffusion transfer and a replenisher having an inorganic salt concentration not lower than the inorganic salt concentration of the processing solution, the processing solution comprising an aqueous solution containing 50% by weight ethanol ( twenty five
C), wherein the replenisher contains at least one amino alcohol having a pKa value of less than 9 and one having a pKa value of 9 or more, and the replenisher contains at least one amino alcohol having a pKa value of 9 or more.