JPH06266068A - Method for processing medical silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable rapid processing to be carried out in an automatic developing machine comparatively slow in a conveying speed even in a small replenishing amount of a developing solution and a fixing solution by processing the specified medical silver halide X-ray photograph at a specified conveying speed for a specified time length with each specified replenishing amount of a development processing solution and a fixing solution with the roller-conveying type automatic developing machine. CONSTITUTION:The X-ray photographic sensitive material has, on both sides of a transparent support, silver halide emulsion layers containing silver halide grains sensitive to radiation One of the emulsion layers contains the silver halide grains amounting to at least projection areas of >=60% of the those of the total grains comprising flat grains having an average aspect ratio of >=8, and the emulsion layer has a gelatin to silver weight ratio of >=0.8, and a coating amount of silver on each side of the support is <=1.5g/m<2>, and a total gelatin amount in the emulsion layers including a protective layer is <=3.0g/m<2>. This photosensitive layer is processed by using the roller-conveying type automatic developing machine in a conveying speed of <=33mm/sec for the total time length of <=50sec required for the total processes of development, fixing, rinse, and drying, and in replenishing amounts of a developing solution and a fixing solution of 300lm per 1m<2> of the photosensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing medical X-ray photographic light-sensitive materials, and particularly to a method for processing in a short time with a small amount of replenishing processing in a small automatic developing machine (hereinafter, automatic developing machine). Regarding

[0002]

2. Description of the Related Art Reducing the replenishing amount of a processing solution is an important issue in the photographic industry, and for example, replenishing amount reducing techniques are disclosed in JP-A-3-75742, 4-116550, and 4-128837. Further, in recent years, rapid processing has become widespread, and the processing time has been greatly shortened even in the processing of automatic developing machines for various kinds of photosensitive materials. However, with a small automatic processor,
A treatment method that requires a small amount of treatment replenishment and can be treated in a short time has not yet been known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material capable of rapid processing in a small automatic developing machine having a conveying speed of 33 mm / sec or less even when the replenishing amounts of a developing solution and a fixing solution are small. And a processing method thereof.

[0004]

The above object of the present invention is to have a silver halide emulsion layer comprising radiation-sensitive silver halide grains on both sides of a transparent support, wherein at least one emulsion layer is a silver halide grain. Of tabular grains having an average aspect ratio of 8 or more, and gelatin / silver (weight ratio) in the emulsion layer of 0.8 or more,
Roller-conveying automatic development of photographic light-sensitive material for X-rays, characterized in that the amount of coated silver on each side is 1.5 g / m ² or less and the total amount of gelatin including the protective layer is 3.0 g / m ² or less. Using a machine, the conveying speed is 33 mm / sec or less, the total time required for all the steps of development, fixing, washing and drying is 50 seconds or less, and the developer and fixer replenishing amount is 300 ml or less per 1 m ^{2 of} the light-sensitive material. And a method for processing a silver halide photographic light-sensitive material.

The silver halide emulsions preferred in this invention are at least 60% of the total projected area of the silver halide grains.
Is composed of tabular grains having an average aspect ratio of 8 or more. The definition of tabular grains, the method for preparing tabular grains and the method for calculating the average aspect ratio in the present invention are described in JP-B-4-2.
It is described in Japanese Patent No. 3769. In the present invention, it is more preferable that the silver halide emulsion is monodisperse with respect to each of the projected area equivalent diameter of the grain and the thickness of the grain.
JP-A-2-838; U.S. Pat. Nos. 5,147,771; 5,147,772; 5,147,773; 5,1.
71,659; European Patent 0514742A1 discloses a method for preparing a monodisperse tabular emulsion having a variation coefficient of projected area equivalent diameter of 20% or less. Two or more kinds of monodisperse tabular emulsions may be mixed and used. As the halogen composition of the tabular silver halide grains used in the present invention, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and silver chloride can be used. Here, the content of silver iodide is preferably 2 mol% or less, and particularly preferably 1 mol% or less. The halogen composition of the tabular grains of the present invention is particularly preferably AgBrCl or AgBrI having a silver iodide content of 1 mol% or less. The tabular silver halide emulsion having a high aspect ratio of the present invention may be a mixture of two or more kinds.

The silver halide emulsion used in the present invention is chemically sensitized. As the chemical sensitization method, known methods such as sulfur sensitization method, selenium sensitization method, tellurium sensitization method, reduction sensitization method and gold sensitization method can be used alone or in combination. Sensitization of sulfur, selenium and tellurium is specifically described in Japanese Patent Application No. 4-222679.

Gelatin of the silver halide emulsion layer of the present invention /
Silver (weight ratio) is 0.8 or more, preferably 0.9 to 1.8.
Is. If it is less than 0.8, the graininess of the developed silver deteriorates, which is not preferable for diagnosis. Coating amount is 1.6g / m ² per side
The following is preferably 1.5 g / m ² or less. In order to obtain a high density with a small amount of silver, it is desirable to use silver halide grains having an aspect ratio of 8 or more, preferably 9 or more and 15 or less. It is particularly preferred that all emulsion layers constituting the light-sensitive material are tabular grains having an aspect ratio of 8 or more. The total amount of gelatin per side is 3.0 g / m ² or less, preferably ^{2.9g / m 2 ~2g / m 2} .

The swelling ratio of the hydrophilic colloid layer is 130% to 2
40% is preferable. If it is less than 130%, fixing failure tends to occur. If it is 240% or more, poor drying tends to occur. Here, the swelling ratio is measured by the method disclosed in JP-A-58-111933.
According to the method of. The hydrophilic colony layer of the light-sensitive material of the present invention preferably has a melting time of 15 to 80 minutes. If it is 15 minutes or less, black spots are likely to occur in the developing process, and if it is 80 minutes or more, the residual color increases. The measuring method of the melting time is as follows. When the silver halide photographic light-sensitive material cut into 1 cm × 2 cm is immersed in a 1.5% by weight aqueous solution of sodium hydroxide at 50 ° C., the silver halide light-sensitive material is formed. It means the time until at least one silver halide emulsion layer begins to melt.

The water content is preferably in the range of 7 g to 16 g / m ² . The method for measuring the water content is described below. 25
A sample of 20 cm x 20 cm exposed under the conditions of ℃ and relative humidity of 70% as much as necessary to obtain the maximum density was processed by Fuji Photo Film Co., Ltd. CEPROS-M (processing speed 45 seconds). ) Is used, and the developing solution and the fixing solution are CE-D-F1.
Using a specified amount of (manufactured by the same company), development is 35 ° C, fixing is 32
C., and tap water at 18.degree. C. is supplied at a rate of 3 liters per minute for automatic development. Remove the drying rack of the automatic processing machine, and take the same sample as the water content measurement sample 1/12
101 sheets are continuously processed at intervals of seconds, the 101st sample is used as a water content measurement sample, and the sample is extracted at the exit of the squeeze rack, and the weight is measured after 15 seconds. (At this time, the power of the drying system is not turned on in advance.) The weight at this time is Ww (g). Next, the sample is sufficiently dried, and then allowed to stand for 1 hour or more at a temperature of 25 ° C. and a relative humidity of 55%, and its weight is measured. This is designated as Wd (g). Water content water content ^{(g / m 2) = (} Ww-Wd) × (10000 cm 2/20
cm x 20 cm). The weight measurement location must be a location where the wind speed is 0.5 m / sec or less.

The image silver tone of tabular grains having a high aspect ratio tends to be yellowish. Especially the average aspect ratio is 15
It is remarkable in the silver halide emulsions having a size of more than 1. It is common practice to correct the yellowish developed silver tone and to color the transparent support blue so that it looks pure black. Further, the hydrophilic colloid layer including the emulsion layer may contain a cyan and / or magenta dye for adjusting a silver image color tone. Typical dyes are Japanese Patent Application Nos. 3-352857 and 4
-90658. For cyan and magenta dyes added to the hydrophilic colloid layer, R concentration and G, respectively
The concentration is preferably 0.12 or less.

There are no particular restrictions on the various additives and the like used in the photographic light-sensitive material of the present invention, and for example, those described in the following relevant parts can be used. 1) Antifoggant, Stabilizer JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column . 2) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94249, page 6, lower left column, line 15 to Page 11, right upper column, line 19 3) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 4) Surfactant JP-A-2-68539, page 11, upper left column, line 14 Antistatic agent to page 12, upper left column, line 9 5) Matting agent, slipping agent JP-A-2-68539, page 12, upper left column, line 10 Plasticizer, same as upper right column, line 10; page 14, lower left column, line 10 to lower right column, line 1 6) Hydrophilic Colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 7) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 8) Support, JP-A-2-68539, page 13, upper right column, line 7 to line 20. 9) Crossover JP-A-2-264944, page 4, upper right column, line 20: From cut method, page 14 upper right column. 10) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9 No. 3-24537, page 14, lower left column to page 16, lower right column. 11) Polyhydroxy JP-A-3-39948, page 11, upper left column to benzenes, page 12, lower left column, EP Patent No. 452772A. 12) Layer structure JP-A-3-198041.

In the automatic developing machine of the present invention, although the dry-to-dry process is quick within 50 seconds, the linear velocity for conveying the photosensitive material is 33 mm / sec, particularly preferably 28 mm / sec-10 mm.
It is characterized by being / sec. The composition of the treatment liquid used in the present invention, the treatment method, and the washing method are described in JP-A-3-249755, page 3, upper right, line 19 to page 6, upper left 1.
You can refer to the third line. Further, regarding the whole processing method, JP-A-4-29135 and JP-A-4-53
The processing method of 948 can be used.

Dry to Dr in the sensitive material / processing system of the present invention
When processing for 50 seconds or less at y, a roller made of rubber as described in JP-A-63-151943 is applied to the roller at the outlet of the developing tank in order to prevent development unevenness peculiar to rapid processing. Kaisho 63-15194
It is desirable that the discharge flow rate for stirring the developing solution in the developing solution tank as described in No. 4 is 10 m / min or more. Further, for rapid processing as in the present invention, especially the constitution of the rollers of the fixing solution tank is opposed to increase the fixing speed and, in the case of a sensitizing dye-containing photosensitive material, to elute the dye. More preferably, it is a roller.
Drying is performed at about 40 ° C to 100 ° C, and the drying time is appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 20 seconds.
Seconds is fine. Drying is performed by a method using hot air, a method using a far-infrared heater, a method by contact heating of a photosensitive material, or a combination of these three methods. For example, a combination of hot air drying and far infrared drying, and a combination of hot air drying and contact heating drying with a heat roller are particularly preferable.

[0014]

【Example】

Example 1 Preparation of tabular grains 6 g of potassium bromide and average molecular weight of 15 in 1 liter of water.
Thousands of low-molecular weight gelatin (7 g) was added to a container kept at 55 ° C while stirring, and an aqueous silver nitrate solution of 37 cc (silver nitrate 4.00
38 cc of an aqueous solution containing g) and 5.7 g of potassium bromide was added over 37 seconds by the double jet method. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C. and 89 cc of silver nitrate aqueous solution (9.8 g of silver nitrate) was added over 22 minutes. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the pAg at 8.5. Next, 15 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. It was determined for particles having a projected area diameter of 0.6 μm or more and a thickness of less than 0.3 μm. Pure silver bromide tabular grains having an average aspect ratio of 10, an average projected area diameter of 1.2 μm and a diameter variation coefficient of 24% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature is raised to 40 ° C again and 30 g of gelatin is added.
And 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickening agent,
PH 5.90 with caustic soda and silver nitrate solution, pAg 8.2
Adjusted to 5. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. 0.1 mol% AgI fine particles
Then, 0.043 mg of thiourea dioxide was added, and the mixture was kept for 22 minutes for reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and sensitizing dye

[0015]

[Chemical 1]

400 mg of was added. Further, 0.83 g of calcium chloride was added. Subsequently, 1.3 mg of sodium thiosulfate, 2.7 mg of selenium compound-1 and chloroauric acid.2.
6 mg and 90 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. In this way, preparation of tabular grains T-1 was completed.

Selenium compound-1

[0018]

[Chemical 2]

Preparation of Coating Sample A coating sample was prepared by adding the following chemicals to 1 mol of silver halide to prepare a coating solution.・ Gelatin (including gelatin in emulsion) 93.6 g ・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Hardener 1 , 2-Bis (vinylsulfonylacetamido) ethane Addition amount is adjusted so that the swelling rate is 190%.

[0020]

[Chemical 3]

Dye A is added to the above coating solution in an amount of 1 per side.
The dye emulsion A (1) was added so that the amount was 0 mg / m ² .

[0022]

[Chemical 4]

(1) Preparation of Dye Emulsion (1) 60 g of the above dye A and the following high boiling organic solvent A6
2.8g, 62.8g B and 333g ethyl acetate 6
Melted at 0 ° C. Next, 65 cc of a 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 cc of water were added, and the mixture was emulsified and dispersed at 60 ° C. for 30 minutes with a dissolver.
Next, 2 g of the following compound C and 6 liters of water were added, and 4
The temperature was lowered to 0 ° C. Next, using Asahi Kasei's ultrafiltration laboratory module ACP1050, the total amount was concentrated to 2 kg, and 1 g of the compound C was added to obtain a dye emulsion (1). High boiling organic solvent

[0024]

[Chemical 5]

Compound C

[0026]

[Chemical 6]

The surface protective layer was prepared and prepared so that each component had the following coating amount. Contents of surface protective layer Coating amount-Gelatin 0.966 g / m ² -Sodium polyacrylate (average molecular weight 400,000) 0.023 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0 .015

[0028]

[Chemical 7]

Polymethylmethacrylate (average particle size 3.7 μm) 0.087 Proxel (adjusted to pH 7.4 with NaOH) 0.0005

Preparation of Support (1) Preparation of Dye D-1 for Undercoat Layer The following dyes were ball milled by the method described in JP-A-63-197943.

[0031]

[Chemical 8]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. 400 ml of zirconium oxide (ZrO ₂ ) beads (2 mm diameter) were added and the contents were crushed for 4 days.
After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO ₂ beads were removed by filtration. Observation of the obtained dye dispersion showed that the particle size of the crushed dye had a wide distribution with a diameter of 0.05 to 1.15 μm, and the average particle size was 0.37 μm. Further, centrifugation was performed to remove dye particles having a size of 0.9 μm or more. Thus Dye Dispersion D-1
Got

(2) Preparation of support Corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoat liquid having the following composition was applied at an amount of 5.1 cc / m ² . And a wire bar coater, and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0034]

[Chemical 9]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc

[0036]

[Chemical 10]

2,4-Dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc distilled water 900.5 cc A second undercoat having the following composition on the above-mentioned first undercoat layers. Layers are coated on each side so that the coating amount is as described below, and 150 ° C on both sides by the wire bar coater method.
It was applied and dried.・ Gelatin 80 mg / m ²・ Dye Dispersion D-1 (13 mg / m ² as dye solids)

[0038]

[Chemical 11]

Matting agent Polymethylmethacrylate having an average particle size of 2.5 μm 2.5 mg / m ²

Preparation of Photographic Material The above emulsion layer and surface protective layer were coated on both sides of the prepared support by the simultaneous extrusion method. The amount of silver per side is 1.4
It was set to g / m ² .

The coating amount of silver of this light-sensitive material (light-sensitive material) was 1.4 g / one side, m ² , the total amount of gelatin was 2.3 g / one side,
m ² , swelling rate 190%, melting time 60 minutes,
The water content was 11 g / m ² .

Next, the average aspect ratio of the tabular grains is 6.
2. A comparative light-sensitive material which does not belong to the present invention was prepared using a silver halide emulsion having an average projected area diameter of 1.1 μm. In order to obtain the same maximum blackening density, it was necessary to set the coated silver amount on one side to 1.7 g / m ² .
The amount of gelatin in the emulsion layer and the surface protective layer was the same as in the light-sensitive material.

§ Processing The automatic developing machine FPM-1300 manufactured by FUJIFILM Co., Ltd. was modified to increase the film transport speed and dry at 26 mm / sec.
It was possible to process to Dry for 45 seconds. Development temperature during processing is 3
5 ° C., fixing temperature 35 ° C., washing water temperature 18 ° C., washing water amount 3 liters per minute, developer circulating stirring liquid amount was 20 during development.
It was set to liter / min and standby 6 liter / min. The replenishment amount was 12 cc / 10 × 12 inch for the developer and 12 cc / 10 × 12 inch for the fixer.

Treatment liquid <Developer replenisher> Potassium hydroxide 28.0 g Sodium sulfite 75.0 Diethylenetriaminepentaacetic acid treatment 2.0 Sodium carbonate 30.0 Hydroquinone 18.0 Diethylaminoethyl-5-mercaptotetrazole 0.1 Bromide Potassium 1.0 Triethylene glycol 6.0 5-Nitroindazole 0.3 Acetate 40.0 4-Methyl, 4-hydroxymethyl-1-phenyl-3-pyrazolidone 7 Processing aid-I 0.2

[0045]

[Chemical 12]

Make up to 1 liter with water (adjust to pH 10.3 with sodium hydroxide). <Fixer replenisher> Ammonium thiosulfate 96.4 g Ethylenediaminetetraacetic acid / disodium dihydrate 0.025 Sodium metabisulfite 22.0 Make up to 1 liter with water (pH 5.0 with sodium hydroxide).
Adjust to). When the development processing was started, each tank of the automatic processor was filled with the following processing solutions. Developing tank: 4.0 g of potassium bromide and 3.5 g of acetic acid were added to 1 liter of the developer replenisher. Fixing tank: 1 liter of the above fixer replenisher.

Chest Phantom Practical Technique The photosensitive materials − and − were set to an X-ray tube voltage of 120 KV,
Front screen made by Fuji Photo Film Co., Ltd.
HR-4, using HR-8 as a back screen,
Performed chest phantom practice. X Ray Film Super HR-S made by Fuji Photo Film Co., Ltd. 300
Unexposure of 300 sheets, exposing to 300 sheets, developing and fixing solution 10 ×
A total of 600 with a replenishment amount of 12 cc per 12 inch sheet
One sheet was processed. Thereafter, the chest phantom film of the light-sensitive material of the present invention-and the light-sensitive material of the comparison-was processed. With the light-sensitive material of the present invention, a good phantom image was obtained. In the light-sensitive material, defective fixing was recognized.
In addition, the phantom image appeared grainy.

Claims (1)

[Claims] 1. A transparent support having on both sides thereof a silver halide emulsion layer comprising radiation-sensitive silver halide grains, wherein at least one emulsion layer has an average aspect ratio of at least 60% of the total projected area of the silver halide grains. The emulsion layer has a ratio of gelatin / silver (weight ratio) of 0.8 or more, and the amount of coated silver on each side is 1.6 g / m ²
Hereinafter, the total amount of gelatin including the protective layer is 3.0 g / m ² or less, and a photographic light-sensitive material for X-rays is developed by using a roller-conveying type automatic developing machine at a conveying speed of 33 mm / sec or less.・ The total time required for all processes of fixing, washing and drying is 5
A method of processing a silver halide photographic light-sensitive material, which comprises processing with a developer and fixer replenishing amount of 264 ml or less per 1 m ^{2 of} the light-sensitive material for 0 second or less.