JPH06102630A - Method for processing silver halid photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce environmental pollution and to improve uneven density due to processing and to enable rapid processing by regulating the conveyance speed of the photosensitive material, the time length necessary for all the processes, and the replenishing amounts of developing and fixing solutions each to a specified value. CONSTITUTION:The photosensitive material having at least one silver halide emulsion later on a support is processed by a roller-conveying type automatic developing machine. Flat silver halide grains having an aspect ratio of >=2 are contained in the silver halide emulsion layer in a projection area of >=50% of that of the total silver halide grains, and the conveyance speed of the automatic developing machine is regulated to <=33mm/sec. The total time required for all the processes of developing, fixing, rinsing, and drying is controlled to <=50sec. The photosensitive material is processed with a replenishing amount of each of the developing solution and the fixing solution of <=300ml/m<2>, preferably, 60-200ml/m<2>, and the conveyance speed is controlled, preferably, to 28-10 mm/sec.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rapid processing method for a silver halide photographic light-sensitive material and a silver halide photographic light-sensitive material which have low pollution, improve density unevenness occurring during processing, and provide a uniform finished state. is there.

[0002]

2. Description of the Related Art In the photographic industry, reduction of pollution, speeding up, and stabilization of processing are important issues, and many studies have been made so far. For example, JP-A-3-75742, JP-A-4-116550, and JP-A-4-128837 disclose techniques for reducing the replenishment amount of the processing liquid. Regarding the technology for reducing washing water, JP-A-57-8542 and 57-85
43, JP-A-4-151143 and JP-A-4-195040,
No. 4-199151. On the other hand, in recent years, rapid processing has become widespread, and the processing time for automatic developing machine processing of various photosensitive materials has been greatly shortened. When these photosensitive materials having aptitude for rapid processing were processed by various automatic developing machines, even if the total processing time was the same (for example, 46 seconds), density unevenness due to processing strongly occurred depending on the structure of the automatic processor. It was confirmed.

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to the processing of a silver halide photographic light-sensitive material in which the developer replenishment amount and the fixer replenishment amount are small, the pollution is low, the density unevenness at the time of processing is improved, and rapid processing is possible. The present invention relates to a method and a silver halide photographic light-sensitive material.

[0004]

The above object of the present invention is to provide a method for processing a light-sensitive material having at least one silver halide emulsion layer on a support using a roller-conveying type automatic processor. 50% or more of the projected area of all silver halide grains in the silver halide emulsion layer are tabular silver halide grains having an aspect ratio of 2 or more, and the transport speed of the automatic processor is 33 mm / sec or less, and Development, fixing, washing,
The total time required for all the drying steps is 50 seconds or less,
Further, it was achieved by a processing method of a silver halide photographic light-sensitive material characterized by processing with a replenishing amount of a developing solution and a fixing solution of 300 ml or less per 1 m ^{2 of the} light-sensitive material.

In the present invention, the replenishing amount of the developing solution and the fixing solution is 300 ml or less, preferably 50 per 1 m ² of the light-sensitive material.
It is preferable that the amount is from ml to 250 ml, more preferably from 60 ml to 200 ml. The conveying speed of the automatic processor is 33 mm / sec or less, preferably 28 mm / sec to 10 mm / sec.

In order to reduce the loads of the developing solution and the fixing solution and to achieve satisfactory developing property, fixing property and washing property with a small replenishing amount, the coating amount of silver is at least sufficiently high and the covering power is high. Silver halide emulsions are preferred. At least 50% of the total projected area has an aspect ratio of 2
As described above, a silver halide emulsion composed of 3 to 15 silver halide grains is desirable for achieving the object of the present invention. 3 as the average aspect ratio of all tabular grains
It is preferably -15. Average aspect ratio is 15
If it exceeds, the silver tone of the image becomes yellowish, which is not preferable.

[0007] coated silver amount per one side 1.8 g / m ² or less preferably is preferably ^{1.65g / m 2 ~1.0g / m 2} .
If it is 1.0 g or less, a sufficient blackening density cannot be obtained. The total amount of gelatin per side is 3.2 g or less, preferably 3 g /
m ^{2 to 2} g / m ² is preferred. If the amount is 2 g or less, the silver / gelatin ratio becomes high and emulsion pick-off easily occurs.

The swelling ratio is 130% to 250%. Thirteen
If it is less than 0%, fixing failure tends to occur. If it is 250% or more, poor drying tends to occur. Here, the measurement of the swelling ratio is based on the method of JP-A-58-111933. Further, when the thickness of the hydrophilic colloid layer after swelling is 20 μm or less, the effect of the swelling ratio defined above becomes remarkable.

The melting time should be in the range 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. Here, the measuring method of the melting time is 1 cm x 2
When the silver halide photographic light-sensitive material cut into cm is immersed in a 1.5% by weight aqueous solution of sodium hydroxide at 50 ° C.,
It means the time until at least one silver halide emulsion layer constituting the silver halide light-sensitive material begins to melt.

The water content should be in the range of 7 to 16 g / m ² . The method for measuring the water content is described below. 25
A sample of 20 cm × 20 cm exposed under the conditions of temperature of 70 ° C. and relative humidity of 70% as much as necessary to obtain the maximum density was processed by Fuji Photo Film Co., Ltd. automatic processor CEPROS-M (processing speed: 45 seconds). ) Is used, and the developer and fixer are CE-DF
1 (manufactured by the same company) is used in a predetermined amount, development is 35 ° C, fixing is 3
The temperature is 2 ° C., and the washing water is 18 ° C. tap water is supplied at a rate of 3 liters per minute for automatic development. The dry rack of the automatic processor was removed, the same sample as the water content measurement sample was continuously processed at 101 sheets at intervals of 1/12 seconds, and the 101st sample was used as the water content measurement sample. 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, after sufficiently drying the sample, the temperature is 25 ° C. and the relative humidity is 55% for 1 hour or more.
Let stand under the conditions of and measure its weight. Wd this
(G). The water content is determined by water content ^{(g / m 2) = (} Ww-Wd) × (10000 cm 2 / 20cm × 20cm). The weight measurement location must be a location where the wind speed is 0.5 m / sec 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. For example, the additives described in the following relevant parts can be used. Item Relevant part 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, bottom 6 from its production line to page 10, upper right column, line 12, and 3-24537 Page 2, lower right column, line 10 to page 6, upper right column, line 1; page 10, upper left column, line 16 to page 11 lower left column, line 19; Japanese Patent Application No. 2-225637. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 3) Antifoggants and Stabilizers 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 . 4) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, left lower column, line 20; JP-A-3-94 249, page 6, lower left column, line 15 to Page 11, right upper column, line 19 5) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 6) Surfactant JP-A-2-68539, page 11, upper left column, line 14 Antistatic agent to page 12, upper left column, line 9 7) 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 8) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 9) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 10) Support, JP-A-2-68539, page 13, upper right column, lines 7 to 20. 11) Crossover JP-A-2-264944, page 4, upper right column, line 20: From cut method, page 14, upper right column. 12) 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. 13) Polyhydroxy JP-A-3-39948, page 11, upper left column to benzenes, page 12, lower left column, EP Patent No. 452772A. 14) Layer structure JP-A-3-198041.

The automatic processor of the present invention has a Dry to Dry of 50.
The linear velocity for conveying the photosensitive material is 33 mm / sec, particularly preferably 28 mm / sec to 1 even though it is a rapid processing of less than a second.
It is characterized by 0 mm / sec. It is extremely surprising that the occurrence of density unevenness could be significantly suppressed by carrying out the process at a relatively low carrying linear velocity even though it was a rapid process. The composition of the treatment liquid used in the present invention, the treatment method, and the washing method are described in JP-A-3-249.
Reference can be made from page 755, page 3, upper right line 19 to page 6, upper left line 13, line 13. Further, regarding the overall processing method, the processing methods of JP-A-4-29135 and JP-A-4-53948 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 Photosensitive Material) 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. Here, 7 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 6.5 cc of 100% acetic acid solution was added. 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. Physical aging for 5 minutes at the same temperature, then 35 ℃
Lowered the temperature to. Monodispersed pure silver bromide tabular grains having an average projected area diameter of 1.10 μm, a thickness of 0.165 μm and a variation coefficient of diameter of 18.5% 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 (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 220%.

[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. Observing the obtained dye dispersion, the particle size of the crushed dye has a wide range of diameters from 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 1.5
It was set to g / m ² .

The coating amount of silver of this light-sensitive material (light-sensitive material) was 1.5 g / one side, m ² and the total amount of gelatin was 2.4 g / one side.
m ² , swelling rate is 220%, melting time is 45 minutes,
The water content was 12 g / m ² . Further, as a light-sensitive material, a light-sensitive material having the same composition as that of the light-sensitive material was prepared except that the addition amount of the hardener was increased to make the swelling rate 175%. Melting time is 68 minutes, water content is 10g / m ²
Met.

Rapid processing The automatic processor FPM-1300 manufactured by FUJIFILM Corporation was modified to increase the film transport speed and the film transport speed 2
It was possible to process Dry to Dry 45 seconds at 6 mm / second. (Processor- (a). The processor of the present invention) Also, an automatic processor FPM-2 manufactured by Fuji Film Co., Ltd.
000 is modified to dry t at film transport speed of 35 mm / sec.
o Dry 45 seconds can be processed. (Processing machine- (b). Comparative processing machine) The developing temperature during processing was 35 ° C, the fixing temperature was 35 ° C, the washing water temperature was 18 ° C, the washing water amount was 3 liters per minute, and the circulating stirring liquid amount of the developer was Development 20 liters / minute, standby 6 liters /
Set to minutes.

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 Acetic acid 40.0 1-Phenyl-3-pyrazolidone 3.5 Processing aid-I 0.2

[0044]

[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.

[0046]

Evaluation of unevenness in density Two pieces of HR-4 screens made by Fuji Photo Film Co., Ltd. (front and back) were prepared for each of the prepared light-sensitive materials.
So it's normal. 2m from the X-ray tube MTF
Rectangular chart for measurement (made of molybdenum, thickness: 80 μm,
Spatial frequency: 0 lines / mm to 10 lines / mm) was placed, and the above-mentioned photosensitive material / screen unit was placed after the X-ray source. The X-ray tube used is Toshiba Corporation's DRX-37.
24 HD, using a tungsten target, having a focal spot size of 0.6 mm × 0.6 mm, and generating an X-ray through an aluminum equivalent material of 3 mm including a diaphragm. A voltage of 80 KVP was applied to the three phases with a pulse generator, and an X-ray that passed through a filter of 7 cm of water having absorption almost equivalent to the human body was used as the light source. Exposed photosensitive material-,-
Was processed by the above-mentioned processing machine- (a) and processing machine- (b) to evaluate the density unevenness. Here, the density unevenness was evaluated for the level of desensitization and trailing that occurs in the background density when a portion that changes from high density to background density in a rectangular shape passes through the high density portion first. (Exposure was adjusted so that the background density was 0.7 to 0.75) ◯: Occurrence was almost unknown. Δ: Desensitization is slightly generated. The desensitization trail is 0.
It is 5 mm or less. Practically acceptable. X: Desensitization is clearly visible. The trail extends over 1 cm. Not practically possible. The results are summarized in Table I.

[0048]

[Table 1]

Claims (3)

[Claims] 1. A method of processing a light-sensitive material having at least one silver halide emulsion layer on a support using a roller-conveying type automatic processor, wherein all silver halide grains in the silver halide emulsion layer are processed. 50% or more of the projected area of is a tabular silver halide grain having an aspect ratio of 2 or more, the conveying speed of the automatic developing machine is 33 mm / sec or less, and in all steps of development, fixing, washing and drying. Total time required is 5
A method of processing a silver halide photographic light-sensitive material, characterized in that the processing time is 0 second or less, and the amount of replenishing developer and fixing solution is 300 ml or less per 1 m ^{2 of the} light-sensitive material. 2. The total amount of gelatin on the coated surface containing the silver halide emulsion layer (on one side when the emulsion layers are coated on both sides) is from ² g to 3.2 g / m ² , and the coated silver amount is from 1.8 g. 1.0 g /
The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the method is m ² . 3. A swelling ratio of 130% to 250%, a film thickness after swelling is 20 μm or less, and a melting time of 15
3. The method for processing a silver halide photographic light-sensitive material according to claim 2, wherein the water content is from 7 minutes to 80 minutes and the water content is from 7 g to 16 g / m ² .