JPH0473864B2 - - 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 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 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 solvent, and the unexposed halide emulsion layer is Silver is converted to 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 to reproduce documents, create lithographic printing plates,
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 treatment solutions have been proposed, such as those shown in 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. For example, as shown in FIG. 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 in the water from the processor, PH decreases due to absorption of carbon dioxide gas in the air, and if it contains developing agent, its oxidation, etc. These factors are intricately intertwined and cause the running It is thought that the processing characteristics are changing. Against this background, the inventor of the present invention has continued research to improve running performance, and as a result, has achieved running performance that is much longer than conventional running life without using conventional replenishment fluids. I found a way to process it. (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 photographic properties 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 treatment liquid for silver complex salt diffusion transfer, wherein the treatment liquid contains at least one amino alcohol, and the treatment liquid is concentrated by the running treatment. This was achieved by a treatment method characterized by diluting the concentration of inorganic salts with water. The present invention will be explained in more detail below. The use of amino alcohol in the DTR treatment liquid is described in the above-mentioned patent specifications and other patent specifications and is well known. The running processing method of the present invention is considered to be based on the following effects. In other words, common DTR processing solutions include sulfites and thiosulfates, and in the case of so-called alkaline activating solutions that do not substantially contain developing agents, inorganic salts such as sodium phosphate (N _a3 PO ₄ ) are used. Contains a large amount of These inorganic salts play an important role in DTR development, but they
It has the property of suppressing the swelling of the gelatin layer of the positive material, that is, suppressing the amount of liquid absorbed by the processing liquid. Therefore, the concentration of these inorganic salts increases by the amount of water evaporated during the running process, and development is inhibited. In addition, the processing liquid that has absorbed carbon dioxide gas in the air during the running process
As the pH decreases, the concentration of inorganic salts further increases due to the gradual increase in carbonate. Furthermore, as a result of the processing agent being consumed by the running process, the concentration, especially the quantitative balance, of the processing agent changes. Among these fluctuation factors in the running process, in response to an increase in the inorganic salt concentration, an amount of water equivalent to the evaporated water is replenished to adjust the inorganic salt concentration to the initial, ie, new solution. However, in the processor shown in Figure 1, it is difficult to control the salt concentration, and especially in running processing, there is a processing liquid carried out by negative material and positive material, so the amount of evaporated water and pressure separation are difficult to manage. There are some aspects that are difficult. Therefore, there is often an oversupply or shortage of water, and the salt concentration becomes low or high, making it impossible to obtain the desired results. However, the present inventor has discovered that by replenishing water during running processing with a processing solution containing amino alcohol, these difficulties can be overcome, and the results remain unchanged from the initial photographic properties for an extremely long period of time, for example, one month. I found that I could get more than that. The reason for this is not clear, but it is thought to be as follows. That is, it is known that amino alcohol acts not only as an alkaline agent but also as a silver halide solvent and as a preservative. The present inventor also discovered that inorganic salts act as a swelling agent for the gelatin layer, that is, they act as a swelling agent for the gelatin layer. This means that when running processing is performed with a processing solution that does not contain amino alcohol, the concentration of inorganic salts increases due to the evaporation of water from the processing solution, and the peeling of negative and positive materials developed with that processing solution is slower than with a fresh solution. This can be understood from the fact that the above-mentioned difficulty in peeling is alleviated in a treatment liquid containing amino alcohol, whereas the above-mentioned difficulty in peeling becomes difficult. Therefore, amino alcohol works to alleviate the swelling inhibition of the gelatin layer not only in a new solution containing a relatively high concentration of inorganic salts, but also in inorganic salts concentrated by running processing, and also works to reduce the limit concentration of inorganic salts. When inorganic salts are diluted in excess of (this varies depending on the type, amount, etc. of salts and amino alcohols), and the inorganic salt concentration is higher than the initial concentration (that is, the dilution is insufficient), it works in the same way as above. In addition, their properties as alkaline agents, silver halide solvents, and preservatives are auxiliary (in some cases, main) so that they have virtually no effect on composition changes and pH reductions caused by excessive dilution and running. This seems to be working on the target. From the above, in the treatment method of the present invention, in order for the properties of the amino alcohol to have a desirable effect on the fluctuation factors of the running treatment,
It will be understood that combined with water replenishment, it has become possible to perform a dramatic running process. Therefore, in the present invention, since the amount of processing solution carried out for negative materials and positive materials can be roughly known in advance, the amount of water evaporated due to the remaining amount of processing solution concentrated by running processing can also be roughly known. You can dilute it appropriately using the amount of water as a guide. Dilution may be performed at any time during the running process, depending on the type and amount of salts, but it is generally best to perform dilution when approximately 10% or more of the water has evaporated, and repeat this operation. The processor may be modified to provide periodic or automatic dilution, for example by attaching a water replenishment container. The "water" used for dilution in the present invention is essentially free of processing agents. however,
In cases where the compound does not substantially affect the quality characteristics of DTR development, or even if the compound does affect the above, the effect is in a negligible amount, an aqueous solution containing such a compound may also be included in the present invention. It should be understood that water is included in the term ``water.'' The higher the concentration of inorganic salts in the new solution, the earlier and more frequently it needs to be diluted during a run. Therefore, the DTR treatment liquid used in the present invention is
It is better to use as little inorganic salt as possible. In particular, phosphates (e.g. N _a3 PO ₄ ), which are well known as alkaline agents for alkaline activation solutions, have traditionally been used in amounts of 0.15 to 0.25 mol per 1 treatment solution, but since they have a strong swelling suppressing effect as described above, Preferably, the amount is less than or equal to about 0.1 mole. Sulfite is about 0.2 to about 0.5 mol/thiosulfate is about 0.2 to about 0.5 mol/
A range of 0.02 to about 0.15 mol/l is preferred, and a total amount of inorganic salts is preferably in a range of about 0.3 to about 0.7 mol/l. 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/. Furthermore, if desired, thickening agents such as carboxymethyl cellulose,
Hydroxyethylulose, antifoggants such as potassium bromide, benzotriazole, toning agents such as 1-phenyl-5-mercapto-tetrazole, developer modifiers such as polyoxyalkylene compounds, quaternary ammonium salts, development nuclei such as UK It can contain various compounds used in DTR processing liquids, such as those described in Patent No. 1001558 and, if necessary, 1-phenyl-3-pyrazolidones. The amino alcohol contained in the DTR treatment liquid used in the present invention is a primary, secondary, or tertiary amine compound having at least one hydroxyalkyl group, preferably a secondary or tertiary amino alcohol. Amino alcohol has the following general formula (A)
This includes compounds represented by 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-dimethylethanolamine, 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. It is particularly preferable that the amino alcohol contains at least one amino alcohol having a PK _a value of less than 9 and at least one amino alcohol having a PK a value of 9 or more in an aqueous solution containing 50% by weight of ethanol (25° C.). 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 Himaruzen Co., Ltd.) and can be easily measured. The pKa value in the present invention is defined as that measured at 25° C. in a 50:50 by weight mixture of ethanol and water. Amino alcohols with a pKa value of less than 9 and amino alcohols with a pKa value of 9 or more are used in processing liquids that have absorbed carbon dioxide gas during running treatment, that is, carbonic acid (H ₂ CO ₃ ).
For pKa values, lower and higher pKa values, respectively.
An amino alcohol of less than 9 ensures the developing ability of the processing solution, and an amino alcohol of 9 or more improves photographic properties during low-temperature processing and prevents contamination (positive material) during running processing. There was found. Generally, amino alcohols having one hydroxyalkyl group have a pKa of 9 or more, and amino alcohols having two or three hydroxyalkyl groups have a pKa of less than pKa. These amino alcohols have a molar ratio of 2:
Preferably, the ratio is 8 to 8:2.
The amount of amino alcohol used is in the range of 0.2 to 2.0 mol, preferably 0.3 to 1.5 mol, per 1 treatment liquid, whether used alone or in combination. The PH of the processing solution is the PH that activates the developing agent, usually about 10 to 14, preferably about 11 to 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 silver halide content generally ranges from 0.5 g to 3.5 g/m ² in terms of silver sulfate. It is coated with 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 silver halide emulsion layer in negative materials and the image receiving layer in positive materials both contain hydrophilic colloid substances, such as gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose, and dextrin. , 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 an a-olefin polymer, 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-mercaptotetrabul 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 with 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 solutions [A] and [B] were prepared. [A] [B] Na ₃ PO ₄・12H ₂ O Na ₂ SO ₃ Na ₂ S ₂ O ₃・5H ₂ O KBr 1-Phenyl-5-mercaptotetrazole N-Methylethanolamine Diethanolamine Make 1 with water 75 60 20 1 0.1 - - 75g 60g 20g 1g 0.1g 0.3 mol 0.1 mol Put 1 each of processing solutions [A] and [B] into a commercially available processor as shown in Figure 1 (for example, One Step S Processor, trade name of Mitsubishi Paper Industries). 30 sets of negative and positive materials (both A4 size) 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 lines/inch contact screen using a conventional plate making camera. The processing liquid temperature is 20℃, and the transfer time is
Peeled off in 60 seconds. Running treatment test Each treatment solution treated as described above (remaining volume approximately 900ml)
The processor was left open for 10 days at 23°C and 65% RH with the lid removed. The remaining volume in each case was approximately 710 ml. 100 ml of water was added to each of the processing liquids, and when the water was added, one set of negative material and one set of positive material were processed in the same way. Table 1 shows the maximum reflection density value and the quality of halftone dots.
Peelability and transfer unevenness: ○ (good), △ (bad),
The results are shown as × (very poor).

[Table] The results in Table 1 show that by performing running treatment with treatment solution [B] and replenishing water, each evaluation characteristic is restored, and there is tolerance to the amount of water used for dilution. Example 2 The method of Example 1 was followed for the following treatment liquid [C]. However, after running, water 200% every 10 days.
Table 2 shows the evaluation when I continued running while processing 30 sets of negative and positive materials after replenishing ml. The opening time was under the conditions of 23°C and 65%RH. [C] Na ₂ SO ₃ 45g NaS ₂ O ₃・5H ₂ O 16g Hydroxyethyl cellulose 3g KBr 1g 1-phenyl-5-mercaptotetrazole 0.05g N-methylethanolamine 0.4 mol N-methyldiethanolamine 0.4 mol Adjust to 1 with water

[Table] According to the processing method of the present invention, various properties such as density, contrast, peelability, transfer unevenness, etc. are almost the same as new solutions, and are far superior to conventional solutions (until the processing agent is practically used up). It is understood that long-term running treatments (which may be possible) are possible. Example 3 The direct positive silver halide photosensitive material described in Example 4 of JP-A-59-45441 was used as a negative material, and a gelatin image-receiving layer containing palladium sulfide nuclei (3 g/m ² ) was used as a positive material. was provided on a polyester film. Use the following [D] to [F] as the processing solution at a processing temperature of 15
The procedure of Example 2 was followed except that the treatment was carried out at °C. The results are shown in Table 3. [D] [E] [F] NaOH 10 5 5g NaSO ₃ 60 60 60g NaS ₂ O ₃・5H ₂ O 20 20 20g Hydroquinone 12 12 12g 1-phenyl-3-pyrazolidone
1 1 1g 1-phenyl-5-mericaptotetrazole
0.1 0.1 0.1g KI 0.1 0.1 0.1g Hydroxyethyl cellulose
2 2 2g N,N-diethylethanolamine
− − 0.3 mol N-ethyldiethanolamine
−0.6 Set to 1 with 0.3 mol water

[Table] After processing 30 sets of negative and positive materials with the new solution, the remaining amount of the solution was about 870 ml, and when the solution was left for two weeks, the remaining amount of the solution was about 620 ml. Therefore,
Water replenishment is 250 ml added. (F) Effects of the Invention According to the running treatment method of the present invention, it has become possible to perform running treatment for a significantly longer period of time than in the past while maintaining the good properties of the new solution.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view of a typical processor that can be used in the present invention. 1... Squeegee roller, 2... Partition plate, 3
...Lid, 4...Processing liquid.

Claims (1)

[Claims] 1. In a method of running treatment using a treatment liquid for silver complex salt diffusion transfer, the treatment liquid contains an amino alcohol with a pka value of less than 9 and an amino alcohol with a pka value of 9 or more in an aqueous solution containing 50% by weight ethanol (25 ° C.). A treatment method comprising at least one of each of the inorganic salts and diluting the concentration of the inorganic salts concentrated by running treatment with water.