JPH0915797A - Method of preserving processing solution for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To prevent occurrence of corrodion of a film container and film peeling and pinholes due to vibrations and storage at high temperature by storing the processing for the photosensitive material in the container composed of a specified multilayer film. CONSTITUTION: The processing solution is preserved by using a flexible container composed of the multilayer film comprising at least one polyolefin layer prepared by a metalocene catalystic method and at least one polyethylene terephthalate layer. At that time, the processing solution for the photosensitive material to be used is not especially limited. The developing solution for graphic arts photosensitive material and black-and-white photosensitive material may contain hydroxtbenzene type developing agents, 1-phenyl-3-pyrazolidone type and p-amino-phenol type developing agents, sulfite type preservatives, alkaline agents, pH buffers, such as carbonates, borates, or phosphates, silver halide development inhibitors, glycol type organic solvents, mercapto type or other organic development inhibitors, and further, color toners, surfactants, and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preserving a processing solution for silver halide photographic light-sensitive materials, and more specifically, a good photograph can be obtained by using the processing solution for silver halide photographic light-sensitive materials after storage over time. The present invention relates to a method for preserving a processing solution for silver halide photographic light-sensitive materials, which uses a flexible processing solution container having excellent performance, excellent disposability, and environmental suitability.

[0002]

2. Description of the Related Art Processing solutions for silver halide photographic light-sensitive materials are concentrated solutions in the fields of graphic arts, X-ray, general black-and-white photography and color photography.
It is often supplied as a liquid product such as parts liquid and used liquid.

These processing solutions for silver halide photographic light-sensitive materials are stored in bottle-type, cubic-type, film-type, standing pouch-type, etc. containers. In recent years, cubic-type, Flexible containers such as a film type and a standing pouch type are often used, and among these, a flexible container of a film type and a standing pouch type is particularly used.

Further, the processing solution for silver halide photographic light-sensitive materials is stored for a long period of time, or its contents are deteriorated in the process of transportation or storage, or the container is damaged due to vibration,
In some cases, liquid leakage or the intended photographic performance may not be obtained during actual use.

[0005]

Conventionally, a flexible container made of a multilayer film made of nylon or a vinylidene chloride-coated nylon and a polyethylene film or a polyethylene-vinyl acetate alcohol copolymer film has been proposed. It is used a lot,
In the case of a multilayer film of a film made of a material other than nylon and a polyethylene film or a polyethylene-vinyl acetate alcohol copolymer film, the polyethylene film or the polyethylene-vinyl acetate alcohol copolymer film must have a certain thickness or more. I could not reduce the amount.

Halogen using a flexible container made of a film and a multilayer film, which can maintain the original performance of a processing solution for silver halide photographic light-sensitive materials and further reduce the amount of resin, and which can reduce the amount of resin. Development of a method for storing a processing solution for silver halide photographic light-sensitive materials is desired.

[0007]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide an improved flexible container which replaces nylon, which is free from corrosion, film peeling, damage and pinholes of a film container during storage under vibration or high temperature. The second purpose is to provide an improved flexible container instead of nylon which gives good photographic characteristics even under long-term storage. The third object is to provide an excellent method for preserving the processing solution for silver halide photographic light-sensitive materials. The third object is to provide an excellent processing solution for silver halide photographic light-sensitive materials using a flexible container capable of reducing the amount of resin. There is a storage method provided.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a container filled with a processing solution for silver halide photographic light-sensitive material,
A silver halide characterized by being stored using a flexible container characterized by comprising a multi-layer film having at least one polyolefin resin layer by a metallocene catalyst method and at least one polyethylene terephthalate resin layer. This has been achieved by the method of storing processing solutions for photographic light-sensitive materials.

The polyethylene film prepared by the metallocene catalyst method is described in "Convertec, March 1995". That is, a flexible container made of a multilayer film of a polyolefin resin prepared by a metallocene catalyst method and a K-PET resin (a polyethylene terephthalate resin layer is coated with vinylidene chloride) is a polyolefin resin prepared by a conventional method and a K-PET resin. It is superior in strength compared to a flexible container made of a resin multilayer film. Furthermore, the oxygen permeability of the container is 50 ml /
It is preferably m ² · atom · day (temperature 20 ° C, relative temperature 65%) or less.

The processing solution for silver halide photographic light-sensitive material used in the present invention is not particularly limited in terms of composition. Developers for graphic arts light-sensitive materials and black-and-white light-sensitive materials include dihydroxybenzene-based developing agents, 1-phenyl-3-pyrazolidone-based or p-aminophenol-based developing agents, sulfite-based preservatives, alkali agents, carbonates or boric acid. A pH buffering agent such as a salt or a phosphate, a halide-based development inhibitor, a glycol-based organic solvent, a mercapto-based or other organic development inhibitor may be contained, and if necessary, a color tone agent, a surfactant,
A defoaming agent, a water quality adjusting agent, a hardener, an amino compound and the like may be included.

Further, fixing solutions for graphic arts light-sensitive materials and black-and-white light-sensitive materials include thiosulfate-based fixing base agents, sulfite-based preservatives, pH buffering agents such as acetic acid and boric acid, dibasic acids, and aluminum salts. It may contain a film forming agent, a pH adjusting agent such as sulfuric acid, and may further contain a fixing accelerator and a water quality adjusting agent, if necessary.

Further, the stabilizing solution for the graphic arts light-sensitive material and the black-and-white light-sensitive material may contain a mercapto compound, a sulfite, a water quality adjusting agent, a pH buffering agent and a pH adjusting agent, and if necessary, a thiosulfate, It may contain a lithium salt, a magnesium salt or the like.

Further, the color developing solution for a color light-sensitive material is p
-A phenylenediamine-based color developing agent, a hydroxylamine-based preservative, a sulfite-based preservative, a halide-based development inhibitor, a pH buffering agent such as a carbonate, and an alkaline agent, and may further contain a fluorescer as necessary. It may contain a photowhitening agent, a surfactant, a water quality modifier, an amino compound, and an antifoaming agent.

Further, the bleaching agent for color light-sensitive material may contain a bleaching main agent such as an aminopolycarboxylic acid type iron complex salt, a bromide, a nitrate and a pH adjusting agent, and further, if necessary, a bleaching accelerator, acetic acid or a nitric acid. A pH buffer such as basic acid and a water quality adjusting agent may be contained.

Further, the bleach-fixing solution for color light-sensitive materials contains a bleaching agent such as an aminocarboxylic acid type iron complex salt, a thiosulfate type fixing agent, a sulfite preservative, and a pH of acetic acid or a dibasic acid.
It may contain a buffering agent and a pH adjusting agent, and may further contain a bleaching accelerator and a water quality adjusting agent as required.

Further, the fixing solution for color light-sensitive material may contain a thiosulfate-based fixing main agent, a sulfite-based preservative, a pH buffering agent such as acetic acid or a dibasic acid, and a pH adjusting agent. A fixing accelerator and a water quality adjusting agent may be included as necessary.

Further, the stabilizing solution for a color light-sensitive material contains a mildew-proofing agent or anti-bacterial agent, a water quality adjusting agent, acetic acid or a dibasic acid.
It may contain a buffering agent, a pH adjusting agent, and a surfactant, and may further contain an organic-based hardening agent, if necessary.

[0018]

EXAMPLES Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. [Example 1] The following developer for graphic arts was prepared. Developer: anhydrous sodium sulfite 120.0 g hydroquinone 75.0 g N-methyl-p-aminophenol sulfate 0.6 g potassium bromide 13.5 g boric acid 30.0 g ethylenediaminetetraacetic acid disodium 1.5 g 3-diethylamino-1,2 -Propanediol 25.0 g Potassium hydroxide 90.0 g Sulfosalicylic acid tripotassium salt 60.0 g Water was added to adjust to 1.0 l pH 11.8.

10 l of the developing solution was placed in a four-sided seal type 10 l flexible container (double bag) A, B and C made of the following materials, and the strength of the container and the change in photographic performance of the developing solution were examined by the following tests. The side in contact with the developing solution was a linear low density polyethylene film 70μ.

[Table 1] LLDPE: Linear low-density polyethylene LDPE: Low-density polyethylene EVA: Polyethylene-vinyl acetate copolymer K-PET: Vinylidene chloride-coated polyethylene terephthalate LLDPEm: Metallocene-catalyzed low-density polyethylene

The containers A, B, and C were examined for changes in strength and photographic performance of the developer by the following tests. In addition, the linear low-density polyethylene film 70 μ was used for the side in contact with the developing solution. Drop test Put in a 10l cardboard box and fix it with taping.
The strength was examined by continuously dropping from the height of m 5 times. Transportation test The device was mounted on a transportation truck, and pinholes after running 2000 km were examined using a penetrant flaw detection liquid. Leaving test After being left to stand naturally for 6 months, the change in photographic performance was examined, and the liquid leakage state of the container was further examined. Heat resistance test After using the constant temperature and humidity chamber at 60 ° C and 80% for 1 week,
The change in photographic performance was examined, and the liquid leakage state of the container was further examined. For each test, five of each container were used for photographic performance, and one of the five was selected and examined. The photographic performance was examined using a commercially available photographic film for graphic arts. The results obtained are shown below.

Drop test

[Table 2] As is clear from Table 2, the container C of the present invention is excellent in strength despite the thin polyethylene layer.

Transport test

[Table 3] As is clear from Table 3, the container C of the present invention is excellent in strength despite the thin polyethylene layer.

Leaving test

[Table 4] As is clear from Table 4, the containers A, B and C have excellent oxygen barrier properties. However, liquid leakage occurred in 1 out of 5 containers A.

Heat resistance test

[Table 5] As is clear from Table 4, the container C of the present invention has excellent heat resistance.

Example 2 The following color developing solution for color photographic paper was prepared. Color developer Preservative part Triethanolamine 120.0 g N, N-diethylhydroxylamine 50.0 g Fluorescent brightener (UVITEX MST: Ciba Geigy) 40.0 g Tyrone 3.0 g Sodium chloride 15.0 g Add water Adjust to 700.0 ml pH value 9.8

Alkaline agent part Sodium hydroxide 40.0 g Diethylenetriamine pentaacetic acid 30.0 g Sodium sulfite 1.5 g Potassium carbonate 250.0 g Water is added to adjust to 700.0 ml pH value 14.0 or more

Developing agent part N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulphate (CD-3) 90.0 g sodium sulfite 0.5 g Water was added 250 Adjusted to 0.0 ml pH value 0.8

700 ml of the preservative part and the alkaline agent part of the color developing solution are put in a 3-way type 1.0 l flexible container (single bag) of the following material, and 250 ml of the developing agent part is 500.0 ml of the 3-way type of the following material. It was placed in a flexible container (single bag).

[Table 6] LLDPE: Linear low-density polyethylene LDPE: Low-density polyethylene EVA: Polyethylene-vinyl acetate copolymer K-PET: Vinylidene chloride-coated polyethylene terephthalate LLDPEm: Metallocene-catalyzed low-density polyethylene

The containers D, E, and F were tested in the same manner as in Example 1 to examine changes in the strength of the containers and the photographic performance of the color developing solution. The test is a preservative department in a 10 l cardboard box,
Five alkaline agent parts and five developing agent parts were put in each container, and five containers were prepared for each test. The photographic performance was examined using a commercially available color photographic paper. The results obtained are shown below.

Drop test

[Table 7] As is clear from Table 7, the container F of the present invention is excellent in strength despite the thin polyethylene layer.

Transport test

[Table 8] As is clear from Table 8, the container F of the present invention is excellent in strength despite the thin polyethylene layer.

Leaving test

[Table 9] ◯: No change X: Liquid leakage in 1 out of 5 alkali agent parts As is clear from Table 9, the container F of the present invention is excellent in oxygen barrier and strength.

Heat resistance test

[Table 10] ◯: No change X: Liquid leakage in 1 out of 5 parts of alkali agent part and developer part As is apparent from Table 10, the container F of the present invention has excellent heat resistance.

[Example 3] 700 ml of the preservative and alkaline agent parts of the same color developer as in Example 2 were placed in a standing pouch type 1.0 l flexible container (single bag) made of the following materials, and a developing agent part of 250 ml was used. Was placed in a standing pouch type 500.0 ml flexible container (single bag) of the following materials.

[Table 11] LLDPE: Linear low-density polyethylene LDPE: Low-density polyethylene EVA: Polyethylene-vinyl acetate copolymer K-PET: Vinylidene chloride-coated polyethylene terephthalate LLDPEm: Metallocene-catalyzed low-density polyethylene

The same tests as in Example 2 were carried out on the containers G, H and I to examine changes in strength and photographic performance of the color developing solution. The polyolefin film was provided on the side in contact with each treatment solution. The photographic performance was examined using the same commercially available color photographic paper as in Example 2. The results obtained are shown below.

Drop test

[Table 12] As is clear from Table 12, the container I of the present invention is excellent in strength despite the thin polyethylene layer.

Transport test

[Table 13] As is clear from Table 13, the container I of the present invention is excellent in strength despite the thin polyethylene layer.

Leaving test

[Table 14] ◯: No change X: Liquid leakage in 1 out of 5 alkali agent parts As is clear from Table 14, the container I of the present invention is excellent in oxygen barrier property and strength.

Heat resistance test

[Table 15] ◯: No change X: Liquid leakage in 1 out of 5 parts of alkali agent part and developer part As is apparent from Table 15, the container I of the present invention has excellent heat resistance.

Example 4 The following bleaching solution for color film was prepared. Bleaching solution Ammonium bromide 1500.0 g 1.3-Propylenediaminetetraacetic acid Ferric ammonium monohydrate 2000.0 g 28% ammonia water 140.0 g Glacial acetic acid 600.0 g Ammonium nitrate 1300.0 g Add water to 10.0 l Preparation pH value 4.3

The desilvering performance test was conducted using a commercially available color film. The results obtained are shown below. Drop test

[Table 16] As is clear from Table 16, the container C of the present invention is excellent in strength despite the thin polyethylene layer.

Transport test

[Table 17] As is clear from Table 17, the container C of the present invention is excellent in strength despite the thin polyethylene layer.

Leaving test

[Table 18] As is clear from Table 18, the containers A, B and C are excellent in long-term storage. However, liquid leakage occurred in 1 out of 5 containers A.

Heat resistance test

[Table 19] As is clear from Table 19, the container C of the present invention has excellent heat resistance.

Example 5 The following fixer for graphic arts was prepared. Fixer Ammonium thiosulfate (75% W / V) 500.0 ml Sodium thiosulfate 30.0 g Sodium sulfite 60.0 g Tartaric acid 9.0 g Glacial acetic acid 75.0 g Sodium hydroxide 15.0 g Aluminum sulfate 30.0 g Water was added 1 Adjusted to 0.01 pH value 4.9

The fixing solution (10 l) was placed in the same four-sided type 10 l flexible containers A, B and C as in Example 1, and the same test as in Example 1 was conducted to examine the strength of the container and the change in fixing performance of the fixing solution. The fixing performance test was conducted by using a commercially available graphic arts film. The results obtained are shown below. Drop test

[Table 20] As is clear from Table 20, the container C of the present invention is excellent in strength despite the thin polyethylene layer.

Transport test

[Table 21] As is clear from Table 21, the container C of the present invention is excellent in strength despite the thin polyethylene layer.

Leaving test

[Table 22] As is clear from Table 22, Container C is excellent in oxygen barrier property and strength.

Heat resistance test

[Table 23] As is clear from Table 23, the container C of the present invention has excellent heat resistance.

[0050]

INDUSTRIAL APPLICABILITY According to the present invention, a method for storing a processing solution for a photographic light-sensitive material, which has excellent durability even under conditions of vibration and high temperature and has no change in photographic performance even when the processing solution for a photographic light-sensitive material is stored for a long time Can be provided.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Soriichi Yamagishi 3660 Hachijo, Yashio-shi, Saitama Chugai Photo Pharmaceutical Co., Ltd. (72) Inventor Masahiro Ito 192 Nemoto, Matsudo-shi, Chiba Chugai Photo Pharmaceutical

Claims (2)

[Claims] 1. A processing solution for a silver halide photographic light-sensitive material is stored in a container composed of a multi-layer film having at least one polyolefin resin layer and at least one polyethylene terephthalate resin layer by a metallocene catalyst method. A method for storing a processing solution for a silver halide photographic light-sensitive material, characterized by: 2. A method of storing a processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein the polyethylene terephthalate resin layer is coated with vinylidene chloride.