JPS6128945A - Image stabilizing liquid for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the generation of silver sulfide by incorporating a polymer or copolymer having a pyrolidone nuclear unit in the molecular structure. CONSTITUTION:All of the polymerizable polymers of which the main chain or side chain of the polymer is substd. with the pyrolidone nucleus by as much as an optional number in an optional position are included in the polymer or copolymer having the pyrolidone nucleus in the molecular structure. The polymer or copolymer having 1,000-70,000 average mol.wt. is preferable and is exemplified by poly-N-vinyl-2-pyrolidone, poly-N-(2-acroyloxy)ethyl-1-pyrolidone, poly-N-glycidyl-2-pyrolidone. The amt. of the polymer or copolymer to be used is in a 0.01-100g range for each 1l of the image stabilizing liquid. The stabilizing process using such image stabilizing liquid is executed by processing the photosensitive material with a processing liquid having fixing power then subjecting directly the material to the stabilizing process without a substantial rinsing process. The generation of the silver sulfide which is considered to arise from the decomposition of thiosulfate is thus prevented.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to an image stabilizer used for processing silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials). This invention relates to an image stabilizing liquid that can prevent the occurrence of particles.

[Prior art]

In general, when the light-sensitive material is for color use, it is processed after image exposure in a processing step consisting essentially of one color development step and a desilvering step, followed by a water washing and/or image stabilization step. In the desilvering step, usually
Bleaching and fixing or bleach-fixing are carried out, and thiosulfate is generally used as the fixing agent for these fixing or bleach-fixing processes. 6, the concentration of accumulated silver ions is increasing. For this reason, the applicant has previously proposed an image stabilization process that does not require washing with water after the desilvering process.

The inventor of the present invention discovered the method as a result of continuing research on the proposed technology. That is, it has been found that this anhydrous washing process has a problem in that a silver sulfide-like precipitate is generated over time, which is thought to be caused by the decomposition of the thiosulfate. 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 stabilizing solution is high in 41 processing without water washing, the fluorescent whitening agent is considered to be the cause. We also discovered that there is a problem called bluing, where the black color in the highest density part turns blue in sunlight.

[Purpose of the invention]

The present invention has been made to solve the above problems, and an object of the present invention is to provide an image stabilizer for processing photosensitive materials that can prevent the generation of silver sulfide in the stabilizer over time.

Another object of the present invention is to provide an image stabilizer for processing photosensitive materials that does not cause bluing.

[Summary of the invention]

The above object of the present invention is achieved by an image stabilizer for processing photosensitive materials, which is characterized in that it contains a polymer or copolymer having a pyrrolidone core unit in one molecule structure. A preferred embodiment of the present invention is that the image stabilizing solution is used in a step subsequent to a process that has fixing capabilities and is effective in a process that does not substantially involve water washing.

[Configuration of the present invention]

The present invention will be explained in detail below.

Polymers or copolymers having a pyrrolidone nucleus in the molecular structure used in the present invention (hereinafter referred to as 1 polymer or copolymer of the present invention) Q refers to 1 The main chain or side chain of the polymer is located at any position with a pyrrolidone nucleus It includes all polymerizable polymers in which an arbitrary number of substituents are substituted, and may be a sheep homopolymer or a copolymer obtained by polymerizing 2g or more copolymer components.The latter In some cases, the polymer as a copolymer component has pyrrolidone core units in its molecular structure.

The copolymer obtained by copolymerizing the polymer as a copolymerization component with another polymer that does not have a pyrrolidone core unit in its molecular structure preferably contains 20% or more of 3θ% or more in 1%. It is preferable to include it. In addition, other polymers that do not have a pyrrolidone core unit in their molecular structure to be copolymerized with a polymer as a copolymerization component that has a pyrrolidone core unit in their molecular structure are:
Any material can be used as long as a hydrophilic copolymer can be obtained.

The polymer or copolymer of the present invention has an average molecular weight of i, o
oo to 70,000 is preferable, and typical examples thereof include the following.

[Exemplary compounds]

(1) Poly-N-vinyl-2-pyrrolidone (*Note 1)
) [2] Poly-N-(2-acryloyloxy)ethyl-1-pyrrolidone (3) Poly-N-glycidyl-2-pyrrolidone [4
] Poly-N-allyl-2-pyrrolidone [5] Poly-N,N-dimethyl-N-(3(1-pyrrolidonyl)-2
-Hydroxy]propylamine-N'-acryloimine (6,1 copoly-N-vinyl-2-pyrrolidone/
N-acryloylmorpholine (molar ratio 42:58).

(7) Copoly-N-vinyl-2-pyrrolidone/N-
Acryloylpiperidine (ratio 35:65) [8] Poly-N-vinyl-2-pyrrolidone/N-methacryloyl-2-methylimidazole (
Molar ratio 55:45) (9) Copoly-N-(2-acryloyloxy)-ethyl-2-pyrrolidone/acrylic acid diethylamide (molar ratio 60:40) (10)
Copoly-N-(2-methacrytetrayloxy)ethyl-
2-pyrrolidone/sodium acrylate (molar ratio 75:25) [11] Copoly-N-(3τ7 chloroyloxy)propyl-2-pyrrolidone/methyl methacrylate (molar ratio 65:35) [12] Copoly-N , N-dimethyl-N-[3-(1-pyrrolidonyl)-2-hydroxycoupropylamine-N'-acrylolimine/ethyl acrylate (molar ratio 70:30) [13] Copoly-N-vinyl-2- Pyrrolidone/vinyl acetate (molar ratio 70:30) [14]
Copoly-N-vinyl-2-pyrrolidone/methyl acrylate (molar ratio 70:30) [15] Copoly-N-vinyl-2-pyrrolidone/styrene (molar ratio 80
:20) [16] Copoly-N-vinyl-2-pyrrolidone/acrylic acid amide/N-vinyl-2-methylimidazole (molar ratio 50:30:20) [17] Copoly-N-vinyl-2-pyrrolidone/ N
-(1,1-dimethyl-3-oxo)-butyl-acrylamide (molar ratio 70:30) [18] Copoly-N-allyl-2-pyrrolidone/vinyl acetate (molar ratio 64:36) [19] Copoly- N-vinyl-2-pyrrolidone/4-vinylpyridine (molar ratio 60:40) [20] Copoly-N-vinyl-2-pyrrolidone/ethyl acrylate/acrylic acid monoethanolamine acid (molar ratio 50:45:5 ) [21] Copoly-N-vinyl-2-pyrrolidone/piperidinomaleamic acid piperidic acid (molar ratio 53
:47) (22) Copoly-N-vinylpyrrolidone/4-vinylpyridino-N-methyliodide (molar ratio 42:5
8) (23) Copoly-N-vinylpyrrolidone/thiourea maleate half ammonium salt (molar ratio 60:40) *Note (1) Exemplary compound 0] HaGeneral Aniline
and Film Coho (Generalanili)
ne and film 0orp,) to P%'P
K-15, PVP K-17, PVP K-30゜PV
PK-60, PVP K-go product base, Beanie Nissf Japan ■ (BASFAktiengese
From LL+chaft), Koliton 12°! I)”
N17. :+lJ tons25. Koliton 30, Koliton 9
o, Rubisco-A-K-17, Rubisco-30
, Rubiscoll is commercially available under the trade name -90.

The polymer or copolymer of the present invention, as mentioned above, is partially commercially available and can be easily obtained. !
7 (John Wilery and 5ons+I
nc,) Published (1961) by Daplier Earl Sorenson, T. W. Camppel (W.

R, 5orenson + T, W, Oampbel
Preparative, Method, of, Polymer, Chemistry (Preparative Meth
ods of Polymer Chemistry)
It can be easily synthesized according to the method described in .

The uninvented polymer or copolymer may be used alone or in combination of two or more, and the amount used is 1 to 1 of the image stabilizer. Hit 0. It is in the range of OIF to 100I, preferably in the range of o, osg to ltl. 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.

In the stabilization treatment using the image stabilizing solution of the present invention, a photosensitive material is treated with a processing solution having fixing ability, and then the stabilization treatment can be directly performed with the stabilizing solution without performing a substantial water washing treatment. preferable.

Processing with a processing solution having fixing ability and without substantially subsequent washing with water means - bath development, bleaching, fixing,
After bleach-fixing or fixing, the image stabilization treatment of the present invention is directly performed.

Basically, washing treatment is not performed, but - bath development, bleaching, fixing,
This means that a short silver spinning bath, rinsing, etc. for silver recovery may be provided between the bleach-fixing or fixing bath and the stabilizing bath. However, it is preferable that nothing be provided between the processing bath having fixing ability and the stabilization processing step using the image stabilizing solution. For more information on this point, please refer to JP-A-58-1483.
No. 4, No. 58-18631 and No. 58-134636
No. 1 is known in each specification and can also be referred to in the present invention.

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. Alternatively, the effect of combined use with a copolymer 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 regarding the components other than the above-mentioned non-inventive composition components and usage examples, please refer to JP-A-58-14834 and JP-A-58-58 by the present applicant. No. 105145.

Reference may be made to the techniques described in Japanese Patent Application No. 58-134634, Japanese Patent Application No. 58-18631, and the aforementioned Japanese Patent Application No. 58-58693.

In addition, information on the color development, bleaching, and fixing (or bleach-fixing) treatments used prior to the treatment with the stabilizer of the present invention, the state value and processing temperature of the stabilizer of the present invention, etc. are also provided in the above-mentioned publications or specifications. The technology described in the book can be referred to, but 1. When the color developing solution contains a generally known fluorescent brightener, 1. When processing with a stabilizing solution containing the polymer or copolymer of the present invention, blue As mentioned above, a particularly remarkable effect of preventing ing can be obtained.

The stabilizer according to the 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.

〔Example〕

Next, the present invention will be explained in detail by way of examples.

The present invention is not limited to these examples.

Example-1 After soft printing on color paper manufactured by Konishiroku Photo Industry Co., Ltd.
Continuous replenishment processing using an automatic developing machine (referred to as running processing)
did. The treatment steps and composition of the treatment liquid at this time are as follows.

Standard processing step [U color development 38°C 3 minutes 30 seconds (2)
Bleach fixing 33℃ 1 minute 30 seconds
I (3) Stabilization treatment 25℃~30℃ 3 minutes (4)
Drying 75°C to 100°C for about 1 minute Processing solution composition <Color developer tank liquid> Color developer replenisher> Bleach-fix tank liquid><Bleach-fix replenisher A> Bleach-fix replenisher B> Stable tank liquid and Replenisher> Fill an automatic processor with the above color developing tank solution, bleach-fixing tank solution and stabilizing tank solution, and add the above color developing replenisher and bleach-fixing replenisher A, every 3 minutes while processing the color paper. A running test was conducted while replenishing B and stable replenisher through the indicator cup. The amount of replenishment is 190-1 as the amount of replenishment to the color development tank (color paper lv & this) respectively, 190-1 as the amount of replenishment to the bleach-fixing tank, 50-1 each of bleach-fix replenisher A and B as the amount of replenishment to the stabilization bath The liquid was replenished by 400 yen.

The stabilization baths of the automatic processor are the first to third tanks in the direction of flow of the photosensitive material.

A multi-vessel countercurrent system was used in which replenishment was performed from the final tank, and overflow from the final tank was allowed to flow into the previous tank, and this overflow liquid was also allowed to flow into the previous stage tank.

Continuous processing was performed until the total replenishment amount of stabilizing solution became three times the capacity of the stabilizing tank. At this time, it will be tripled ~, just before the face,
Stabilizer overflow was collected. As shown in Table 1, the sampled compound (Ll(D P
VP K-17 (neutral in text - ○)) was added in varying amounts, placed in an Erlenmeyer flask, and placed at room temperature or in each of the stabilization treatment baths 1 to 3 as shown in Table 1 (PVP K-15
was increased little by little, the color vapor was treated at this time, and the spectral reflectance at 340 nm was measured to evaluate bluing, and the results are shown in Table 1.

Table-1 (Note-1) O: No precipitation 3° Δ: Very little precipitation.

X: Precipitation present.

(Note-2) Blueing is stronger as the reflectance at 340 nm is higher.

As is clear from Table 1, compared to the case where PVP K-15 is zero, in the present invention with PVP K-15 added,
It turns out to be very favorable both for precipitation and for blueing. In particular, it is found that the addition amount is preferably 0.01.97° C. or higher, and it is extremely preferable that the addition amount is 0.01.97° C. or higher, and o.1y71 or higher. Also, PvP in Blueing is 0.2g7
At 27% or less of 1 or more, there was no problem at all when visually inspected under sunlight. The addition amount of 20171 had the drawback that the color paper was slightly sticky, and when it was 15 og/l, the color paper was very sticky. Here, "stickiness" refers to the property of sticking to other objects, especially when humidity is high.

Example 2 The same experiment as in Example 1 was conducted using the same formulation as in Example 1 except that ammonium hydroxide (25% aqueous solution) was removed.

As a result 1, among the effects of PVP K-15 of the present invention, the prevention effect on precipitation prevention and bluing was slightly smaller when the amount of PVP K-15 added was small. % relative humidity for two weeks, it was found that the addition of an ammonium compound was effective in the present invention because the generation of yellow stain was slightly greater than that of ammonium addition.

Example-3 3j for black and white paper! Image agent (manufactured by Konishiroku Photo Industry Co., Ltd.) IQ
The solution was dissolved in 1 liter of water, and 2 g of a fluorescent whitening agent (trade name: Keikoru PAN, manufactured by Nippon Soka Kogyo Co., Ltd.) was added. Using this developer and fixer Conifix (manufactured by Konishiroku Photo Industry Co., Ltd.), black and white paper Yoshino F8 Vapor (manufactured by Konishiroku Photo Industry Co., Ltd.) was used.
it) was developed.

After fixing, without washing with water, continuously add 0.0% of the stabilizing solution of Example-1 and Rubiscoll = 17 (neutral content - (1)) to this solution.
5#/1 stabilizer solution was treated with 3d for each lρ. The two types of stable solutions after treatment were placed in an IL Erlenmeyer flask and stored at room temperature. As a result, the stable solution in which -17 was not added to Rubiscoll produced a precipitate after the first month, whereas the stabilizer solution in which -17 was added to Rubiscoll did not cause any problems. Thus, it has been found that the effect of preventing precipitation on 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.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Nobuaki Sakaguchi (1 other person)

Claims (2)

[Claims] (1) An image stabilizer for processing silver halide photographic materials, which contains a polymer or copolymer having a pyrrolidone core unit in its molecular structure. (2) A silver halide photograph according to claim 1, wherein the image stabilizing solution is used in a step subsequent to a processing solution having a fixing ability and is suitable for use in a development process that does not substantially involve washing with water. Image stabilizer for processing photosensitive materials.