JPH05281671A - Package for direct positive type silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the fluctuation in sensitivity and the degradation in density by long-term preservation by enclosing a deoxidizing agent and an oxygen detecting agent together with a direct positive type silver halide photographic sensitive material film into the package. CONSTITUTION:The deoxidizing agent and the oxygen detecting agent are enclosing together with the previously fogged direct positive type silver halide photographic sensitive material into the package. Namely, the deoxidizing agent and oxygen detecting agent which are recently established as one of food preservation techniques are enclosing and packaged, which the remaining oxygen is absorbed and the inside of the packaging container is maintained in a deoxidized and phototight state at the time of phototightly deaerating and packaging the silver halide photographic sensitive material having the previously fogged direct positive type silver halide photographic emulsion layers. Ordinary and common oxygen absorbents are usable as the deoxidizing agent in such a case. Oxidation reduction dyestuff, such as methylene blue, new methylene blue or safranine T, is dissolved in an alkaline soln. of reducing sugar and this soln. is impregnated in marketed filter paper and is dried to prepare a oxygen detecting agent paper piece. This paper piece is stuck as the oxygen detecting agent to the deoxidizing package.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prefogged package for a direct positive type silver halide photographic light-sensitive material, and more particularly to a package for a direct positive type silver halide photographic light-sensitive material having good storage stability. ..

[0002]

BACKGROUND OF THE INVENTION Normally, when a silver halide photographic light-sensitive material is exposed and developed by a light source in the light-sensitive wavelength range of the light-sensitive material, the degree of blackening increases with an increase in the amount of exposure and the amount of exposure is maximized. When the exposure amount is further increased after reaching, the phenomenon that the degree of blackening is reduced is observed, and this phenomenon is called solarization.

Therefore, when a suitable fog such that the blackening density reaches a maximum value is previously given to the silver halide emulsion optically or chemically, solarization occurs by exposure and a direct positive image is obtained. Obtainable. As is well known, a light-sensitive material utilizing such a reversal phenomenon is called a direct positive type silver halide photographic light-sensitive material. This kind of direct positive type silver halide photographic light-sensitive material is used for reproduction of various photographs, but especially for medical X-ray photography, the preservation period of the photograph (original image) used for diagnosis is stipulated by law. Therefore, when a patient is transferred to another hospital or diagnosed or treated at another facility, a duplicate photograph with faithful reproducibility to the original image is provided to the facility so that the patient does not need to be re-photographed. The exposure dose has been reduced.

Further, the spread of modalities for diagnostic imaging such as X-ray CT (Computed Tomography), MRI (Magnetic Resonance Imaging) and CR (Computed Radiography) has led to the dualization of diagnosis and treatment. Accelerating the replication of diagnostic images.

Further, the spread of these image diagnostics has led to an increase in the processing amount of the light-sensitive material, leading to the spread of ultra-rapid processing of 60 seconds or less, and the silver halide photographic light-sensitive material for producing a duplicate image under the same processing conditions. Has been desired. Therefore, the direct positive type photosensitive material is provided with high sensitivity, multi-gradation and good reproducibility in the rapid processing.

The silver halide grains, which are a constituent of the direct positive photographic light-sensitive material, form fine silver nuclei on the crystal surface by a reducing agent to form fog nuclei, which are destroyed by moisture and oxygen. It is known. Therefore, oxidation during storage causes deterioration of the photographic characteristics.

The silver halide grains, which are a constituent of the photographic light-sensitive material, undergo physical ripening in the presence of a protective colloid such as gelatin, the crystals thereof grow, and chemical ripening gives them high photosensitivity. Oxidation during storage causes deterioration of its photographic properties.

Usually, the packaging of the silver halide photographic light-sensitive material is an interleaf paper made of thin paper, which is a sheet-like film such as an X-ray film or a printing film, which is folded back into a V shape. A gripping unit is used to form a packaging unit in which a specified number of gripped sheets are sandwiched between U-shaped thick papers, or a unit of packaging unit excluding the interleaf paper is sandwiched between thick papers to protect it from external impact. However, there is a so-called non-interleaf packaging form in which a barrier bag is sucked and degassed and kept light-tight.

On the other hand, roll-type silver halide photographic light-sensitive materials such as films for indirect photography have a packaging form in which they are kept light-tight in a metal or plastic container.
During deaeration packaging When deaeration is increased by increasing the degree of vacuum by deaeration and suction, it adheres to the barrier bag, or peeling occurs due to the mutual adhesion of the films, so light-tight packaging is performed at a deaeration rate of about 80%. There is.

The direct positive type silver halide photographic light-sensitive material of the present invention also has the conventional packaging form as described above. In the pre-fogged direct positive type silver halide photographic light-sensitive material of the present invention, since the appropriate fog is previously given to the silver halide, the fog may be oxidized and destroyed over time. Therefore, the fog-fogged silver halide photographic light-sensitive material cannot escape oxidation due to oxygen remaining in the barrier bag in the conventional packaging.
The current situation is that sensitivity has changed and maximum density has decreased.

[0011]

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide a package for a highly sensitive direct positive silver halide photographic light-sensitive material, which is free from sensitivity fluctuations and reduction in maximum density even after long-term storage, and It is an object of the present invention to provide a method capable of confirming that the inside of a light-tight package is kept in an oxygen-free state by an oxygen detection agent.

[0012]

The above object of the present invention is to enclose a deoxidizer and an oxygen detector together with a pre-fogged direct positive silver halide photographic light-sensitive material. This is achieved by the material package.

In a silver halide photographic light-sensitive material having a directly fogged direct positive type silver halide photographic emulsion layer,
When the silver halide photographic light-sensitive material is packed in a light-tight degas
In recent years, by encapsulating and packaging an oxygen absorber packaging body, which has been established as one of the food storage technologies, and an oxygen detector, the remaining oxygen is absorbed and the packaging container is deoxidized and kept in a light-tight state. A package for a direct positive type silver halide photographic light-sensitive material was obtained, which was provided with a monitor function for controlling the oxygen state and did not cause deterioration in photographic performance such as sensitivity and maximum density over time.

The present invention will be specifically described below.

The oxygen scavenger which can be used in the present invention is an ordinary oxygen absorber, and examples thereof include ferrous salt, iron powder, nitrite, bisulfite, dithionite, hydroquinone and catechol. Resorcin, pyrogallol, gallic acid, rongalit, ascorbic acid, ascorbate, isoascorbic acid, isoascorbate, sorbose, glucose, lignin, dibutylhydroxytoluene, butylhydroxyanisole, or the oxygen absorber and carbon dioxide absorber and And is known as described in JP-A-2-61148.

The packaging material constituting the breathable pouch which can be used as the oxygen absorber package of the present invention is not particularly limited as long as it has a Gurley type air permeability of 1000 seconds / 100 cc or less.

For example, papers such as Japanese paper, western paper, rayon paper, non-woven fabric using various fibers such as pulp, cellulose and fibers from synthetic resin, and a package obtained by laminating and laminating perforated plastic film, paper and perforated polyethylene film. A material, a packaging material using a microporous membrane, or the like is used. These deoxidized packages are disclosed in, for example, JP-A-2-413 and 2-61148.
No. 2-128676, No. 2-128729, No. 2-268806, etc. Further, a sheet-shaped deoxidizing material as described in JP-A-2-86758 may be used.

The oxygen detecting agent used in the present invention includes:
A redox dye such as methylene blue, new methylene blue, safranin T, or phenosafranine is dissolved in an alkaline solution of reducing sugar, immersed in a commercially available filter paper and dried, and the piece is attached as a detection agent paper piece to a deoxidizing package. These oxygen detectors are known in JP-A 2-167057 and the like.

Further, these oxygen detecting agents may be used by immersing them in a solidification aid and drying them to form powders, granules, tablets or the like. As the solidifying agent, it is preferable to use a generally used granulating aid, and specifically, gelatin, pectin,
Polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate copolymer, polyethylene oxide, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, gum arabic, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxy Polyoxyethylene alkylphenol ethers such as ethylene octylphenol ether and polyoxyethylene nonylphenyl ether can be used.

The deoxidizing package of the present invention is a package in which one sheet of photographic film, one sheet of folded interleaf paper made of thin paper, and a predetermined number of the sandwiched sheets are sandwiched by U-shaped cardboard. Unit, or a predetermined number of sheets excluding the interleaf paper as a packaging unit in which only single leaf interleaf paper is applied only to the surface that contacts the U-shaped cardboard, or a predetermined number of sheets excluding the interleaf paper The packaging unit, which is sandwiched between U-shaped thick paper as a packaging unit, is conditioned at 23 ° C and RH 47% for 2 hours, and is degassed and sealed in a light-proof and moisture-proof sealing bag together with a deoxidizing packaging, and is light-tightly packaged. To do.

The silver halide photographic light-sensitive material to which the package according to the present invention is applied is not particularly limited, and various known silver halide photographic light-sensitive material production techniques, particularly known direct positive type silver halide photographic light-sensitive materials are produced. It can be manufactured using technology.

Due to the above-mentioned reasons, the package of the present invention is particularly effective when used directly in a positive type silver halide photographic light-sensitive material.

For the processing of the silver halide photographic light-sensitive material, known processing agents and processing methods can be used.

[0024]

EXAMPLES The effects of the present invention will be illustrated below with reference to examples. However, the present invention is not limited to the following examples.

Example 1 (Preparation of oxygen absorber package 1) Iron powder having an average particle size of 60 mesh and an average particle size of 100 mesh is a non-woven fabric made of polypropylene fiber FS PIO50, basis weight 70 g / m ² , Gurley air permeability 4 seconds / 100cc (manufactured by Asahi Kasei Co., Ltd.) and put in a Fuji Impulse Sealer F1-K400-5 type shield device (manufactured by Fuji Manufacturing Co., Ltd., sold by Mitsui & Co., Ltd.) as shown in Table 1. Oxygen agent packages AF were obtained.

The seal portion of the polypropylene non-woven fabric is a heat-sealing portion due to the heat-sealing ability of the package itself.

(Preparation of oxygen absorber packaging 2) Non-woven fabric FS PIO50 made of polypropylene fiber, NP sheet S-140, basis weight 20 g / m ² , Gurley type air permeability 20-40 sec / 100 cc (Tokuyama Soda Co., Ltd. porous) Oxygen scavenger packages G to V were obtained in the same manner as in Preparation 1 of the oxygen scavenger package described above except that the oxygen scavenger was replaced with a membrane.

(Preparation of oxygen detector 1) 15 ml of 0.5% aqueous methylene blue solution, 75 ml of 30% aqueous D-fructose solution, 15%
Toyo Filter Paper No. 2 was impregnated with a mixed solution of 10 ml of an aqueous potassium hydroxide solution and then naturally dried, and the obtained filter paper cut into 1 × 3 cm pieces (A) was attached to the oxygen absorber packaging.

(Preparation of oxygen detector 2) 18 ml of 0.7% methylene blue aqueous solution, 25 m of 2.0% phenosafranine aqueous solution
l, a mixed solution of 70 ml of 50% D-glucose aqueous solution and 15 ml of 10% sodium hydroxide aqueous solution was impregnated into Toyo Filter Paper No. 2 and then naturally dried, and the obtained filter paper was cut into 1 × 3 cm (B)
Was attached to the oxygen absorber package. (Preparation of emulsion) Preparation of seed crystal A From cubic grains of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.10 μm by a double jet method while controlling at 60 ° C., pAg = 8.0 and pH = 2.0. The following emulsion was prepared. To the mixed solution, gelatin in which 90% of amino groups had phenylcarbonyl groups condensed was added and stirred for 3 minutes. Then, potassium hydroxide was added in an amount of 0.13 g per mol of silver halide to adjust pH.
I set it to 4.0. After decantation after standing still, 40 ℃
2.1 liters of pure water and 0.25 g of potassium hydroxide per mol of silver halide are added to adjust pH to 5.8 and the mixture is stirred for 5 minutes. After that, nitric acid (1.7N) was added to 1.5 ml per mol of silver halide.
In addition, the pH was adjusted to 4.3 and the mixture was left standing and decanted. Further, add gelatin and potassium hydroxide to 0.2 per mol of silver halide.
g was added, and the pH was adjusted to 5.8 to re-disperse, to obtain seed crystal A.

Growth from Seed Crystal A-1 The above seed crystal was dissolved in a gelatin solution kept at 40 ° C., and ammonia was added to adjust the pH to 8.0. Rhodium trichloride and potassium hexachloroiridate were added to this solution, and 2 minutes later, 1N ammoniacal silver nitrate and 1N potassium bromide aqueous solution were added by the double jet method. The pH during mixing was kept at 8.0 and controlled at EAg-20 mV.
After the mixing was completed, the pH was lowered to 6.0 with acetic acid. Thereafter, desalting was performed in the same manner as in the preparation of seed crystal A to obtain emulsion B.

Growth from seed crystal A-2 Growth from seed crystal A- 1 Instead of the 1N aqueous potassium bromide solution, a 1N aqueous solution of potassium iodide and potassium bromide was used. Emulsion C was obtained in the same manner as above except for the above.

The emulsion thus obtained had a pH of 6.8.
In addition, 0.3 mg of thiourea dioxide, 1.2 mg of sodium thiosulfate, and 2.7 mg of chloroauric acid were added per mol of silver halide at 60 ° C., and ripening was performed until proper fog was obtained.

Emulsion B and Emulsion C which had been matured were mixed at a ratio of 8.5: 1.5 to prepare an emulsion coating solution containing the following additives. The emulsion coating solution thus obtained had a silver content of 3.0 g / m ² per one side of the support, and a protective layer solution having the composition described below together with a hardening agent shown in Table 2 so that the gelatin content was 1.0 g / m ^2. Was simultaneously applied at a speed of 70 m / mim and dried for 2 minutes and 25 seconds to obtain a sample film.

(Formulation of coating solution) Lime-treated ossein gelatin 51g 4-hydroxy-6-methyl 1,2,3a, 7 tetrazaindene 1.2g Silver halide emulsion (silver equivalent) 0.6 mol

[0035]

[Chemical 1]

Nitron 0.05 g Copolymer of styrene and butadiene (average particle size 0.03 μm) 2.5 g Copolymer of styrene and maleic acid 1.5 g 2,2-dihydroxymethyl-1-butanol 7.0 g

[0037]

[Chemical 2]

[0038]

[Chemical 3]

(Composition of liquid for protective layer) Coating liquid Per liter Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g

[0040]

[Chemical 4]

[0041]

[Chemical 5]

[0042]

[Chemical 6]

Ludox AM (colloidal silica [DuPont]) 30 g Polymethacrylate particles (projected area average particle size 3.5 μm matting agent) 1.2 g (deoxidizer package encapsulation package)
5.4 x 30.5 cm, gripped with interleaf paper consisting of thin paper folded back one by one, sample packaging with 100 sheets as packaging unit, and 100 sheets excluding interleaf paper as packaging unit A sample package was created. These sample packages were conditioned at 23 ° C and RH 47% for 2 hours, and the photographic photosensitive film was shielded from light together with the deoxidizing package and the oxygen detection agent piece shown in Table 1, and the moisture-proof sealing bag was degassed and airtightly sealed. Packaged.

[0044]

[Table 1]

(Preparation of comparative packaging sample) As a comparative sample,
The sample film was conditioned under the same conditions as the same interleaf packaging and non-interleaf packaging under the same conditions, degassed and sealed in a light-proof and moisture-proof sealing bag containing no deoxygenation packaging, and similarly light-tightly packaged.

The obtained sample film and the comparative sample were stored at room temperature for 3 days, 100 days, 300 days and 500 days. The sample thus obtained was opened on the 3rd day, 100th day, 300th day, and 500th day, and exposed by applying a sensitometry optical wedge with a flat printer II (sold by Konica Medical Co., Ltd.), Processed for 45 seconds using ultra-rapid automatic processor SRX-501, developer XD-SR, and fixer XF-SR (all manufactured by Konica Corporation), sensitivity of each sample, minimum density, maximum density, gamma Etc.

(Evaluation method) Sensitivity The reciprocal of the light quantity when the optical density obtained by subtracting the base density and the minimum density of the obtained sample gives 1.0 is found, and the sensitivity of sample No. 1 (comparative sample) in Table 2 is 100. Was expressed as relative sensitivity.

[0048] Gamma Gamma showed a density of 1.0 of the characteristic curve in the gamma value of 2.0. That is, tan θ is gamma (γ), where θ is the slope of the straight line connecting the density 1.0 point and the density 2.0 point. Oxygen detectability Regarding oxygen detectability, the storage period and the degree of discoloration of the oxygen detection agent from blue to pink were visually evaluated. The results are shown in Tables 2-5.

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

[0052]

[Table 5]

As is clear from the table, the light-tight and moisture-proof, light-tight packaging containing the deoxidized package shows less change in photographic characteristics after 100 days from the initial packaging to 100 days. In addition, the one that does not contain the deoxidized package is 3
At 100, 300 and 300 days, the color change of the oxygen detector is remarkable as the number of days of storage increases, and the photographic characteristics also change drastically.

[0054]

INDUSTRIAL APPLICABILITY According to the present invention, a light-proof, moisture-proof packaged direct positive type silver halide photographic light-sensitive material containing an oxygen detector and an oxygen scavenger retains its photographic performance even after long-term storage for 500 days, It has been possible to provide a package for a direct positive type silver halide photographic light-sensitive material, which is capable of maintaining the maximum density and the minimum density with high sensitivity and faithfully reproducing the original image.

Further, according to the present invention, it is possible to provide a simple oxygen detecting agent which is effective as an oxygen content monitor.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // G01N 31/00 L 7906-2J

Claims (1)

[Claims] 1. A package for a direct positive type silver halide photographic light-sensitive material, characterized in that a deoxidizer and an oxygen detector are enclosed together with a pre-fogged direct positive type silver halide photographic light-sensitive material.