JPH0377982B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a processing method using an image stabilizer used for processing silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials), and in particular to a method for preventing the formation of precipitates due to the contamination of thiosulfates in fixing agents. The present invention relates to a processing method using an image stabilizer that can prevent [Prior Art] Generally, when a color photosensitive material is used, after image exposure, it is processed in a processing process whose basic steps are a color development process and a desilvering process, followed by water washing and/or desilvering process.
Or processed by an image stabilization process. In the desilvering process, bleaching and fixing or bleach-fixing are usually performed, and thiosulfate is generally used as the fixing agent for these fixings or bleach-fixing. The concentration of accumulated silver ions is increasing due to low replenishment. For this reason, the present applicant has previously proposed an image stabilization process that does not particularly require water washing in the image stabilization process after the desilvering process. As a result of continuing research on the proposed technology, the inventor discovered the following. That is, it has been found that this anhydrous washing treatment has a problem in that a precipitate such as silver sulfide, which is thought to be generated by decomposition of thiosulfate, occurs over time. It has also been found that this problem similarly occurs with image stabilizers after fixing black-and-white photosensitive materials. On the other hand, when the salt concentration of the image stabilizer is high, especially in processes that do not involve washing with water, there is a problem that is thought to be caused by the fluorescent whitening agent, which is so-called bluing, where the black color in the highest density part turns blue in sunlight. I also realized that there was a problem. [Object of the Invention] The present invention has been made to solve the above problems, and an object of the present invention is to provide a processing method using an image stabilizer for processing photosensitive materials, which can prevent the generation of silver sulfide in the stabilizer over time. Our goal is to provide the following. Another object of the present invention is to provide a processing method using an image stabilizer for processing photosensitive materials that does not cause bluing. [Summary of the Invention] The object of the present invention is to develop a silver halide photographic light-sensitive material and, after processing it with a processing solution having fixing ability, to process the material in a plurality of processing baths without going through a subsequent washing step. In a method for processing a silver halide photographic light-sensitive material in which a stabilization treatment step is performed, a stabilization replenisher containing a polymer or copolymer having a pyrrolidone core unit is added to the stabilization solution used in the stabilization treatment step. When replenishing the post-bath and treating the stabilizing solution in the post-bath by flowing it countercurrently into the pre-bath, make sure that the stabilizing solution contains 0.1 g/l or more of a polymer or copolymer having a pyrrolidone core unit. This is achieved by a characteristic method for processing silver halide photographic materials. In a preferred embodiment of the present invention, the stable replenisher contains an ammonium compound, and the processing solution having fixing ability contains a thiosulfate. [Structure of the present invention] The present invention will be described in detail below. The polymer or copolymer having a pyrrolidone nucleus in its molecular structure used in the present invention (hereinafter referred to as the polymer or copolymer of the present invention) has a pyrrolidone nucleus in its main chain or side chain. It includes all polymerizable polymers in which an arbitrary number of positions are substituted, and may be a homopolymer thereof or a copolymer obtained by polymerizing two or more types of copolymer components. In the latter case, the polymer as a copolymer component that has a pyrrolidone core unit in its molecular structure is copolymerized with another polymer that does not have a pyrrolidone core unit in its molecular structure and is copolymerized with the polymer as a copolymerization component. At least 20% in the copolymer obtained
The content is preferably 30% or more, particularly 30% or more. In addition, other polymers that do not have a pyrrolidone core unit in their molecular structure to be copolymerized with the polymer as a copolymerization component that has a pyrrolidone core unit in their molecular structure include those that can obtain a hydrophilic copolymer. Any can be used. The polymer or copolymer of the present invention has an average molecular weight of
The number is preferably 1,000 to 70,000, and typical examples include the following. [Exemplary compounds] [1] Li-N-vinyl-2-pyrrolidone (*Note 1) [2] Li-N-(2-acryloyloxy)ethyl-1-pyrrolidone [3] Li-N-glycidyl-2- Pyrrolidone [4] Li-N-allyl-2-pyrrolidone [5] Li-N,N-dimethyl-N-[3(1-pyrrolidonyl)-2-hydroxy]propyl-amine-N'-acrylolimine [6] Poly-N-vinyl-2-pyrrolidone/N
-Acryloylmorpholine (molar ratio 42:58) [7] Poly-N-vinyl-2-pyrrolidone/N
-Acryloylpiperidine (molar ratio 35:65) [8] Li-N-vinyl-2-pyrrolidone/N-
Methacryloyl-2-methylimidazole
(molar ratio 55:45)

[9] Poly-N-(2-acryloyloxy)-
Ethyl-2-pyrrolidone/acrylic acid diethylamide (molar ratio 60:40) [10] Poly-N-(2-methacryloyloxy)
Ethyl-2-pyrrolidone/sodium acrylate (molar ratio 75:25) [11] Poly-N-(3-acryloyloxy)
Propyl-2-pyrrolidone/methyl methacrylate (molar ratio 65:35) [12] Poly-N,N-dimethyl-N-[3-(1
-pyrrolidonyl)-2-hydroxy]-propylamine-N'-acrylolimine/ethyl acrylate (molar ratio 70:30) [13] Poly-N-vinyl-2-pyrrolidone/vinyl acetate (molar ratio 70:30) [14] Poly-N-vinyl-2-pyrrolidone/methyl acrylate (molar ratio 70:30) [15] Poly-N-vinyl-2-pyrrolidone/styrene (molar ratio 80:20) [16] Poly-N -Vinyl-2-pyrrolidone/acrylic acid amide/N-vinyl-2-methylimidazole (molar ratio 50:30:20) [17] Poly-N-vinyl-2-pyrrolidone/N
-(1,1-dimethyl-3-oxo)-butyl-
Acrylamide (molar ratio 70:30) [18] Poly-N-allyl-2-pyrrolidone/vinyl acetate (molar ratio 64:36) [19] Poly-N-vinyl-2-pyrrolidone/4
-Vinylpyridine (molar ratio 60:40) [20] Poly-N-vinyl-2-pyrrolidone/ethyl acrylate/acrylic acid monoethanolamine acid (molar ratio 50:45:5) [21] Poly-N-vinyl -2-pyrrolidone/piperidinomaleamic acid piperidic acid
(Molar ratio 53:47) [22] Poly-N-vinylpyrrolidone/4-vinylpyridino-N-methyl iodide
(Molar ratio 42:58) [23] Poly-N-vinylpyrrolidone/thiourea maleate half ammonium salt
(Mole ratio 60:40) *Note (1) Exemplary compound [1] is manufactured by General Aniline & Film Corp.
aniline and film Corp.) from PVP K-15,
PVP K-17, PVP K-30, PVP K-60,
The product name of PVP K-90 is also from BASF Aktiengesellschaft,
It is commercially available under the trade names of Kollidon 12, Kollidon 17, Kollidon 25, Kollidon 30, Kollidon 90, Rubiscoll K-17, Rubiscoll K-30, and Rubiscoll K-90. The polymer or copolymer of the present invention can be easily obtained as some of it is commercially available as described above, and can be easily obtained from John Wilery and Sons, Inc.
Inc.) Published (1961) by D. A. R. Sorenson, T. D. Campbel (WR
Preparative Methods of Polymer Chemistry, by John Sorenson, TWCampbell
It can be easily synthesized according to the method described in J. Chemistry). The polymer or copolymer of the present invention may be used alone or in combination of two or more, and the amount used is in the range of 0.1 g to 100 g per liter of image stabilizing solution. The polymer or copolymer of the present invention may be added to the stable tank liquid, or may be added to the tank replenishment liquid to replenish the stable tank liquid, or both may be used in combination. It's okay. Further, examples of the fixing agent used in the processing liquid having fixing ability include thiosulfate, and when this is used, the effects of the present invention are effectively exhibited. Other compounds that can be used in the image stabilizer of the present invention include ammonium compounds described in Japanese Patent Application No. 58-58693. The effect of combined use with copolymers is remarkable.
In addition, commonly known stabilizer additives can be used. The stabilizing liquid used in the present invention is essentially a water washing substitute liquid, and for the components other than the above-mentioned composition components of the present invention and examples of use, please refer to Japanese Patent Application Laid-Open No. 58-14834 and No. 58-58-1 by the present applicant. No. 105145, No. 58-134634
Reference may be made to the techniques described in Japanese Patent Application No. 58-18631 and the aforementioned Japanese Patent Application No. 58-58693. For example, the stabilizer used as ^a substitute for washing with water is
Refill with ~2.5 ml, preferably 50 ml~1,
More preferably, 50ml to 200ml is replenished. Further, the color development, bleaching, and fixing (or bleach-fixing) treatments used prior to the treatment with the stabilizer of the present invention, as well as the PH value and processing temperature of the stabilizer of the present invention, etc., are also discussed in the above-mentioned publications or specifications. However, if the color developing solution contains a generally known fluorescent brightener, the blue color may be removed when processed with a stabilizing solution containing the polymer or copolymer of the present invention. As mentioned above, a particularly remarkable effect of preventing ing can be obtained. The stabilizer of the present invention may be used in any processing of silver halide light-sensitive materials. That is, it may be used for processing color photosensitive materials containing color couplers, or it may be used for processing ordinary black and white photosensitive materials. [Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 Color paper manufactured by Roku Konishi Photo Industry Co., Ltd. was subjected to a continuous replenishment process (referred to as running process) after printing with an automatic developing machine. The treatment steps and composition of the treatment liquid at this time are as follows. Standard processing steps [1] Color development 38℃ 3 minutes 30 seconds [2] Bleach-fixing 33℃ 1 minute 30 seconds [3] Stabilization treatment 25℃~30℃ 3 minutes [4] Drying 75℃~100℃ approx. 1 Separation solution composition <Color development tank liquid> Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride 0.2g Potassium carbonate 30.0g 3-Methyl-4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)-alinin sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) (trade name Keikoru PK-Conc (manufactured by Shin Nisso Kako Co., Ltd.)) 1.0g Hydroxylamine sulfate 3.0g 1-hydroxyethylidene-1,1-diphosphonic acid 0.4g hydroxyethyliminodiacetic acid 2.5g Magnesium chloride hexahydrate 0.7g 1,2-dihydroxybenzene-3,5-disulfonic acid-di Sodium salt 0.2g Add water to make 1, then add KOH and H ₂ SO ₄ to PH10.20
shall be. <Color developer replenisher> Benzyl alcohol 20.0ml Ethylene glycol 10.0ml Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g 3-Methyl-4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)-alinin sulfate 7.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) (trade name Keikol PK-Conc (manufactured by Shin Nisso Kako Co., Ltd.)) 2.5g 1 -Hydroxyethylidene-1,1'-diphosphonic acid 0.5g Hydroxyethyliminodiacetic acid 3.0g Magnesium chloride hexahydrate 0.8g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g Water Add 1 and adjust the pH to 10.70 with KOH. <Bleach-fix tank solution> Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to PH7.1 with potassium carbonate or glacial acetic acid Add water to bring the total volume to 1. <Bleach-fixing replenisher A> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 260g Potassium carbonate 42g Add water to bring the total amount to 1. The pH of this solution is 6.7±0.1. <Bleach-fix replenisher B> Ammonium thiosulfate (70% solution) 500ml Ammonium sulfite (40% solution) 250ml Ethylenediaminetetraacetic acid 17g Ice Acetic acid 85ml Add water to bring the total volume to 1. The pH of this solution is 5.3±0.1. <Stable tank fluid and replenisher fluid> 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4-isothiazolin-3-one
0.02g Ethylene glycol 1.0g 2-octyl-4-isothiazolin-3-one
0.01g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5g BiCl ₃ (45% aqueous solution) 0.65g MgSO ₄ 7H ₂ O 0.2g Ammonia water (ammonium hydroxide 25% aqueous solution) 2.5g Nitrilotriacetic acid trisodium salt 1.5g Adjust to 1 with water and adjust to PH7.0 with sulfuric acid. Fill the automatic processor with the color developer tank solution, bleach-fix tank solution, and stability tank solution of the upper machine, and add the color developer replenisher and bleach-fix replenisher A and B mentioned above every 3 minutes while processing the color paper. A running test was performed while replenishing the stable replenisher through a metered cup. The amount of replenishment is 190ml per ^1m2 of color paper to the color development tank.
The bleach-fix tank was replenished with 50 ml each of bleach-fix replenisher A and B, and the stabilization treatment bath was replenished with 400 ml of stable replenisher. The stabilization processing baths of the automatic processor are the first to third stabilization tanks in the direction of the flow of the photosensitive material, and the final tank is replenished, and the overflow from the final tank is allowed to flow into the preceding tank. Furthermore, a multi-tank countercurrent system was adopted in which this overflow liquid also flows into the preceding tank. Continuous processing was carried out until the total replenishment amount of stabilizing solution was three times the capacity of the stabilizing tank. At this time, the stabilizing solution overflow was collected from just before the volume increased three times. Exemplary compound [1] PVP K-17 (note (1) in text) was added to the collected stabilizer overflow as shown in Table 1.
Add in different amounts and put it in an Erlenmeyer flask.
It was stored at room temperature and the results are shown in Table-1. In addition, PVP K-15 was added in small amounts to each of the stabilization treatment baths 1 to 3 as shown in Table 1. At this time, color paper was treated, and as an evaluation of bluing, spectroscopy was performed in the exposure density area (black area). Measure the reflectance and measure the spectral reflectance at 340 nm, and display the results.
Shown in 1.

[Table] As is clear from Table 1, compared to the case where PVP K-15 is zero, the present invention in which PVP K-15 is added is very favorable for both precipitation and bluing. I understand that. Especially when the amount added is
It turns out that 0.1 g/or more is extremely preferable.
Furthermore, in blueing, when the PVP was 0.2 g/min or less and 27% or less, there were no problems when visually inspected under sunlight. It should be noted that when the amount added was 20 g/a, the color paper was a little sticky, and when the amount was 150 g/a, it was very sticky. Here, "stickiness" refers to the property of sticking to other objects, especially when humidity is high. Example 2 Ammonium hydroxide (25
The same experiment as in Example 1 was conducted using the formulation except for % aqueous solution). As a result, among the effects of PVP K-15 of the present invention, it was found that prevention of precipitation and bluing were
When the amount of PVP K-15 added was small, the prevention effect was slightly smaller, and when this sample was left at 60℃ and 80% relative humidity for two weeks, yellow stain generation was slightly higher than when ammonium was added. It has been found that the addition of ammonium compounds is effective in the present invention. Example 3 Developer for black and white paper (manufactured by Konishiroku Photo Industry Co., Ltd.)
Dissolve 1 part of water in 1 part of water, add fluorescent brightener (trade name)
2 g of Keikoru PAN (manufactured by Shin Nisso Kako Co., Ltd.) was added. Black and white paper Yoshino FS paper (manufactured by Konishiroku Photo Industries, Ltd.) was developed using this developer and the fixing agent Konifix (manufactured by Konishiroku Photo Industries, Ltd.).
After fixing, the stabilizer solution of Example 1 (stable tank solution and replenisher solution) was continuously added without washing with water, and 0.5 g/Rubiscoll K-17 (note (1) in the text) was added thereto. 3 m ² of each was treated. After running treatment in the same manner as in Example 1, the two types of stabilizers after treatment were placed in an Erlenmeyer flask and stored at room temperature. As a result, the stabilizing solution to which Rubiscoll K-17 was not added produced a precipitate after the first month, whereas the stabilizer to which Rubiscoll K-17 was added had no problems. From this, it was found that the anti-precipitation effect of the stabilizer of the present invention is effectively exhibited even in the processing of black-and-white light-sensitive materials. Furthermore, no bluing was observed in the stabilizer according to this example.

Claims (1)

[Claims] 1. After developing a silver halide photographic light-sensitive material and treating it with a processing solution having fixing ability, a stabilization treatment process consisting of a plurality of processing baths is carried out without going through a post-washing process. In the method for processing a silver halide photographic light-sensitive material, a stabilization replenisher containing a polymer or copolymer having a pyrrolidone core unit is added to the stabilization solution used in the stabilization treatment step in a bath after the stabilization treatment bath. After the stabilization of the after-bath, the stabilizing solution contains 0.1 g/l of a polymer or copolymer having a pyrrolidone core unit.
A method for processing a silver halide photographic material, characterized by containing the above. 2. The method for processing a silver halide photographic material according to claim 1, wherein the stable replenisher contains an ammonium compound. 3. A method for processing a silver halide photographic material according to claim 1 or 2, wherein the processing liquid having fixing ability contains a thiosulfate.