JPH0444734B2 - - Google Patents

Description

[Detailed description of the invention]

The principle of the silver complex diffusion transfer method (hereinafter referred to as the DTR method) is described in US Pat. No. 2,352,014, and there are many other patents and documents, and it is well known. In other words, under the DTR method,
Silver complex salts are imagewise transferred from the silver halide emulsion layer to the image-receiving layer by diffusion, and they are converted into a silver image, often in the presence of physical image 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 part 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. 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). . 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.
Various types of processors have been designed and put into practical use by manufacturers in other countries, but in general, with some exceptions, temperature control is not performed, and processing at room temperature is common. . Furthermore, the conveyance speed and path length in the developer vary depending on the processor. 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. Although these are very serious issues, they have been ignored because the DTR method relies on a delicate balance between chemical development, dissolution, diffusion, and physical development, which is difficult to control. This is probably because it was thought to exist. Furthermore, another practical problem with the DTR system is the following. That is, in order to satisfy the above-mentioned quality to some extent, the formulation composition of each product has been studied and put into practical use as a combination of a negative material, a positive material, and a DTR processing liquid. That is, as a negative material,
Low-sensitivity products for contact printing, high-sensitivity products for camera work, products using direct positive emulsion, positive materials that use reflection density, and transmission density, and DTR processing liquids. Various materials and processing solutions are selected and combined depending on the method and manner of use, such as those containing a developing agent and those not containing a developing agent.
If any one of the positive materials, negative materials, and processing solutions that have been combined to obtain the highest quality is used as a substitute for another combination product, each combination product has the disadvantage that the original maximum quality cannot be obtained. It was hot. It would be desirable if a versatile processing solution could be obtained that exhibits the above-mentioned good properties for any negative or positive material. The purpose of the present invention is to maintain good color tone with high density, high contrast, and high resolution, without quality deterioration depending on the types of negative materials and positive materials and their combinations, and even when processing conditions change or running processing is performed. An object of the present invention is to provide a processing solution and a processing method for a silver complex diffusion transfer method, which can obtain a high-quality positive material without silver images and background stains. The above object of the present invention is to contain at least the following (A) to (F) per liter, and the total of (A) and (B) to be 0.4 to
0.8 mol, and the molar ratio of (B) to (A) is 2.0
It has been found that this can be achieved by creating a processing solution for silver complex diffusion transfer which is characterized by exceeding the above. (A) MOH (M is alkali metal) 0.05-0.2 mol (B) Alkanolamine
0.25 to 0.7 mol (C) Sulfite 0.4 to 0.7 mol (D) Thiosulfate 0.02 to 0.08 mol (E) P-dihydroxybenzene 0.07 mol or more (F) Benzotriazole 10 ^-4 to 10 ^-2 mol (A) As an alkali agent, sodium hydroxide,
Potassium hydroxide, etc. As the alkanolamine (B), there are compounds represented by the following general formula. (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-
Examples include aminoethylethanolamine and N,N-diethylethanolamine.
Particularly preferred are secondary or tertiary alkanolamines. Examples of the sulfite (C) include sodium sulfite and sodium hydrogen sulfite. Examples of the thiosulfate (D) include sodium thiosulfate and potassium thiosulfate. Examples of P-dihydroxybenzene (E) include hydroquinone, chlorohydroquinone, and methylhydroquinone. The benzotriazole (F) includes compounds represented by the following general formula. (In the formula, R ₁ , R ₂ , R ₃ , R ₄ are hydrogen atoms, alkyl groups, alkoxy groups, halogen atoms, acylamido groups, sulfonamide groups, cyano groups, sulfo groups, carboxy groups, alkoxycarbonyl groups, aryl group, nitro group, aminocarbonyl group,

[Positive material A]

On one side of a 110 g/m ² paper support coated with polyethylene on both sides, an image-receiving layer consisting of a processed product of PVA containing palladium sulfide cores, an ethylene/maleic anhydride copolymer, and gelatin was placed at a dry weight of 3 g/m ²
A positive material A was prepared by providing the following conditions. [Positive material B] Hardened gelatin image-receiving layer containing palladium sulfide nuclei on polyethylene terephthalate film
A positive material B was prepared by providing the amount of 3 g/m ² . [Negative material M] On the same paper support as positive material A, an undercoat layer containing carbon black for anti-halation is provided, and on top of that is silver chloride (silver bromide) with an average particle size of 0.3μ.
A negative material M was prepared by providing an ortho-sensitized gelatin silver halide emulsion layer containing 2.0 g/m ² of silver nitrate (10 mol %). [Negative Material N] Comparative emulsion B described in Example 1 of JP-A-57-96331 was used in place of the emulsion of negative material M to prepare a direct positive silver halide negative material N. Negative materials M and N were attached to a normal plate-making camera, exposed to light, and brought into close contact with positive materials A and B, respectively, for image transfer. The transfer processor uses variable conveyance speed type OSP-12 (trade name) manufactured by Mitsubishi Paper Mills, and the processing liquid temperature,
Set arbitrarily. The transfer time was 60 seconds. For image exposure, a thin line from 10μ to 100μ (every 10μ) and a reflective light wedge are placed on the original, and the exposure amount is controlled from the transferred image wedge.
Further, the ability to form minute images was evaluated from the state of formation of thin lines. The photograph was taken at a 70% reduction in size compared to the original. Evaluation of processing condition latitude The processing liquid temperature was set to 16°C, 23°C, and 30°C, and the conveyance speed was changed to change the residence time of the negative material in the processor liquid by changing the speed. The evaluation setting level is 4 seconds,
6 seconds and 9 seconds. Evaluation of running properties: After processing 60 sets of A-4 size negatives (M) and positives (A) per 2 developing solutions, after aging for 10 openings, transfer processing was performed using various negative and positive systems, and the characteristics ( Transmission density, reflection density) were evaluated. Furthermore, pollution,
Evaluation was made by observing color tone, tone, etc.

[Table] Table 1 shows the developer composition. Treatment liquids D and E are those of the present invention. Table 2 summarizes the treatment results. In this experiment, the conveyance speed of the processor was set so that the residence time of the negative in the liquid was 6 seconds.

【table】

[Table] Processing solutions D and E of the present invention not only provide high transmission density, but also are stable against changes in processing temperature, are free from contamination during low-temperature processing, and have halftone The color was good, the temperature dependence of practical printing sensitivity (expressed as relative sensitivity with the sensitivity at 23°C processing as 100) was small, and the ability to form minute images was excellent. In addition, in similar experiments, regarding the relationship between the processing liquid temperature and the conveyance speed, it was found that with the treatment liquids D and E of the present invention, background yellow contamination was difficult to occur under low temperature and high speed conveyance conditions, while slight yellow staining occurred under high temperature and low speed conveyance conditions. It was confirmed that the decrease in image forming ability was extremely small. Furthermore, Table 3 is a summary of the evaluation of transferred images under running conditions (fatigue fluid).

【table】

[Table] Processing solutions D and E of the present invention also had good running characteristics. Example 2 In the same manner as in Example 1, various properties of the following treatment liquids were examined. (Using negative (M), positive (A), (B))

[Table] The results are evaluated based on the high temperature processability (relatively evaluated from the permeation density at 30℃ processing at a conveyance speed of 9 seconds) and low temperature processability (judging from the occurrence of background yellow contamination at 16℃ treatment at a conveyance speed of 4 seconds). ) and running properties (as in Example 1, judged from yellow background staining) are summarized. With the exception of treatment liquid D of the present invention, problems occurred in some of the characteristics in F- ₁ to F _-4 . This example shows that the objectives of the invention can be achieved within very limited limits. Example 3 In Example 1, in place of N-methylaminoethanol in treatment solution D, diethanolamine or N,N-
Good results were obtained using diethylaminoethanol. Example 4 In Example 1, instead of benzotriazole in treatment liquid D, 5-methylbenzotriazole or 5-
Good results were also obtained with the system in which chlorobenzotriazole was substituted (same weight).

Claims (1)

[Scope of Claims] 1. Contains at least the following (A) to (F) per liter, the total of (A) and (B) is 0.4 to 0.8 mol, and
A treatment liquid for silver complex diffusion transfer, characterized in that the molar ratio of (B) to (A) exceeds 2.0. (A) MOH (M is alkali metal) 0.05-0.2 mol (B) Alkanolamine 0.25-0.7 mol (C) Sulfite 0.4-0.7 mol (D) Thiosulfate 0.03-0.08 mol (E) P-dihydroxybenzene 0.07 More than mol (F) Benzotriazole 10 ^-4 to ^{10 -2} mol